Spill Resistant Surfaces Having Hydrophobic and Oleophobic Borders

ABSTRACT

Described herein are methods for creating spill-proof or spill-resistant surfaces through the use of hydrophobic or oleophobic (H-SH) edges, borders and/or boundaries that contain the water and other liquids within the inside edges, borders and/or boundaries. Also described herein are spill-proof/spill-resistant surfaces. Liquid (e.g., water and other aqueous solutions/suspensions) heights of 3-6 mm on a level planar surface can be sustained by such edges, borders and/or boundaries. The H-SH borders can be created on glass, metal, wood, plastic, and concrete surfaces.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.14/320,315, filed Jun. 30, 2014, issued as U.S. Pat. No. 9,243,175,which is a divisional of U.S. application Ser. No. 13/082,319, filedApr. 7, 2011, issued as U.S. Pat. No. 9,096,786, which is a continuationof International Application No. PCT/U52009/059909, filed Oct. 7, 2009,which claims the benefit of priority to U.S. Provisional Application No.61/159,914, filed Mar. 13, 2009, and U.S. Provisional Application No.61/103,295, filed Oct. 7, 2008. This application is also acontinuation-in-part of U.S. application Ser. No. 14/320,358, filed Jun.30, 2014, which is a divisional of U.S. application Ser. No. 13/082,327,filed Apr. 7, 2011, issued as U.S. Pat. No. 9,067,821, which is acontinuation of International Application No. PCT/U52009/005512, filedOct. 7, 2009, which claims the benefit of priority to U.S. ProvisionalApplication 61/159,914, filed Mar. 13, 2009, and U.S. ProvisionalApplication No. 61/103,295, filed Oct. 7, 2008, the content of each ofwhich applications is hereby incorporated by reference in its entirety.

BACKGROUND

Most liquids, when properly contained, do not give rise to damage,either to the containers in which they are stored or to physicalstructure or equipment that may be used to store the liquids orcontainers of liquids. If spilled, however, the same liquids can cause avariety of problems including contamination, corrosion, and/or damage toequipment or surface that may be used to store the liquids or that comein contact with the spilled liquids. For example, unwanted spills ofwater and other liquids include spills in refrigerators where unwantedmicrobial growth can occur (particularly where liquid runs from shelf toshelf requiring excessive cleaning) and spills on hardwood floorscausing swelling and/or discoloration due to the joints in the woodbecoming wet. Spills on, or in the vicinity of, computers and otherelectronics can cause damage and/or performance problems in theequipment receiving the spilled liquid or other electronic equipment inthe vicinity of the spill. In addition, spills from a drink dispenser inresidential or commercial settings, such as restaurants and fast foodestablishments can lead to hazardous situation including microbialcontamination and situations where individuals may slip and becomeinjured. Where spills of foods and beverages are capable of supportingmicrobial growth, there can be concern over microbial contamination ifthose spills are not properly cleaned, particularly in areas where thepreparation and/or the storage of food occur. Spill may also occur insetting other than those where food is prepared, such as laboratories,lavatories, factory settings and the like.

SUMMARY

Embodiments of this disclosure provide for spill-resistant bordersand/or barriers that may be applied to surfaces. Such spill-resistantborders and barriers can prevent water and other liquids from spreadingor flowing beyond the position of a border on a planer or substantiallyplanar surface that is placed in a substantially level horizontalposition. In embodiments disclosed herein, such borders can prevent thespread of an aqueous liquid until it exceeds a level that is about 4.5mm higher than the surface. In some instances the liquids can be aqueoussolutions, suspensions or emulsions. In other instances, the liquids canbe lipids or oils that are prevented from spreading beyond a borderuntil the level of the oil or lipid exceeds, e.g., 2 mm above thesurface on which the border is formed. In other instances liquid can bean alcohol (e.g., methanol, ethanol, a propanol, a butanol, or apentanol) or a liquid comprising an alcohol (e.g., water and alcoholcombination including alcoholic beverages such as beer, wine anddistilled liquors).

Where the surface, or a portion of the surface, is substantially planar,the spill-resistant border may be placed at or near the edges of theplaner surface or near the edge of the portion that is substantiallyplaner, such that the spill-resistant border surrounds a region of thesurface that has a lower hydrophobicity or lower oleophobicity than thespill-resistant border. Alternatively, the border may be placed so as toform a boundary encompassing one or more portions of the surface thathave a lower hydrophobicity or oleophobicity than the border. Thus,borders may, in some cases, be placed at the edges of (e.g., at or nearthe edges of the treated surface) or form one or more barriersseparating regions of a surface that have lower hydrophobicity than theborders or barriers.

The spill-resistant borders described herein can be made by treating aportion of the surface that will form the border with a variety ofcompositions that comprise agents that cause water, alcohols, oilsand/or other liquids to be retained within the area encompassed by theborder. In some instances, the borders are formed by applying acomposition to a surface that increases the hydrophobicity oroleophobicity of a portion of the surface that will server as a border(e.g., applying a reagent that converts a portion of the surface into amore hydrophobic or more oleophobic surface by covalently attaching oneor more alkyl, fluoroalkyl, or prefluoroalkyl groups to the surface). Insuch embodiments, the border forms a perimeter around at least one areaof the surface that has a lower hydrophobicity or oleophobicity than theborder, (i.e., the resulting border is more hydrophobic and/or moreoleophobic than the area immediately adjacent to it within itsperimeter). Surfaces prepared by such methods are also provided.

Other embodiments provide surfaces comprising a hydrophobic and/oroleophobic spill-resistant border, wherein the border forms a perimeteraround at least one area of the surface that has a lower hydrophobicityand/or lower oleophobicity than the border. In another embodiment, thesurface may comprise a hydrophobic and/or oleophobic spill-resistantborder, wherein said border forms a perimeter around at least two, or atleast three, or at least four, areas of the surface that have a lowerhydrophobicity and/or lower oleophobicity than the border.

Other embodiments will be apparent to skilled artisans from reading thisdisclosure, including the figures and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates multiple embodiments of this disclosure. Shown inFIG. 1 (perspective vertically down) are three glass plates. Panel Adepicts the plates in the absence of liquid and Panel B depicts theplates in the presence of liquid. Plate “(A)” is a “control” glass platewithout any spill-resistant border; plate “(B)” is a glass plate bearinga spill-resistant border that is not visible (i.e., it is invisible);and plate “(C)” is a glass plate bearing a spill-resistant border thatis visible

FIG. 2 shows a schematic illustrating one embodiment of a methodcomprising transformation steps that may be employed to convert a flatglass sheet into a glass sheet having a spill-resistant border. Panels(b)-(f) show steps that may be employed to convert a flat glass panelshown in (a) into a glass sheet having a spill-resistant border (g).

FIG. 3 depicts five different surfaces denoted (A) through (E) withregions (stippled) that have a lower hydrophobicity and/or loweroleophobicity than the spill-resistant border and spill-resistantborders as unmarked (white) regions. In (A), a surface with a spillresistant border in the form of an edge (at its edge) is depicted. (B)shows a surface with a spill resistant border in the form of aspill-resistant edge along with two diagonal spill resistant barriers.The diagonal barriers may retain liquids at the same height as thespill-resistant edge or optionally may have a lesser ability to retainliquids than the border at the edge (i.e., the barrier lines optionallymay retain liquids to lower heights than the border at the edge). (C)shows a surface with a spill resistant border in the form of aspill-resistant edge along with a series of spill resistant barriers inthe form of a grid, where the barrier lines optionally may have a lesserability to retain liquids than the edge. (D) depicts a surface with aspill resistant border in the form of a spill-resistant edge along witha series of partial spill resistant barriers, that optionally may have alesser ability to retain liquids and which may be used to channelliquids toward a drain (or drains), or a site where one or more draintube(s) are connected (black oval). The barrier lines in such anembodiment may extend to the drain. (E) shows a surface with a spillresistant border in the form of a spill-resistant edge along with twodiagonal spill resistant barriers that terminate at a drain (blackoval). The diagonal barriers lines optionally may have a lesser abilityto retain liquids than the edge and can be used to channel or directliquids to the drain. Where drains are attached to a surface, thesurface may be formed inclined or depressed so that the opening of thedrain is lower than the edge of the surface so that liquids will bechanneled to the drain.

FIG. 4 is a plot of etchant pH and its effect on height of waterretained by spill-resistant borders formed with Gelest Inc. silanizingagent SIT 8174 on glass plates.

FIG. 5 shows a comparison of the height of water retained for three setsof glass plates prepared in three different trials using four differenttreatment methods in each trial.

FIG. 6 shows the average height of water retained for each differenttreatment method employed in FIG. 5

FIG. 7 shows the height of water retained by glass plates prepared byfour different treatment methods before and after repeated abrasion witha glass jar.

FIG. 8 in the upper portion shows a photgraph of three glass sheetshaving no order, an invisible border, and a visible border and theirability to retain water. THE LOWER PORTION OF FIG. 8 shows a view of aplate with a visible border at a lower angle that shows the height ofwater retained.

FIG. 9 shows micrographs of glass plates sandblasted with threedifferent grades of abrasive particles (coarse, medium, or fine).

DETAILED DESCRIPTION

Embodiments disclosed herein provide spill-resistant borders that may beformed on a variety of surfaces and methods of their preparation. Anexample of a spill-resistant border is depicted in FIG. 1, where thespill-resistance property of the surface is contrasted with anuntreated, “control” surface.

Embodiments described herein provide, a spill-resistant border that is aportion of surface forming a perimeter around an area of a surface thathas a lower hydrophobicity and/or lower oleophobicity than the border(e.g., the portion of the surface within the perimeter formed by theborder is not treated with a composition that modifies the surface to bemore hydrophobic and/or oleophobic than the border). In otherembodiments, a spill resistant border can be formed on a surface thathas a contact angle with water at room temperature that is less thanabout 10, 15, 20, 30, 40, 50, 60, 70, 80, 90 100, 110, or 120 degrees,and where the border has a contact angle with water at room temperaturethat is greater than the contact angle of water with the surface onwhich it is formed by about 7, 8, 9, 10, 20, 30, 40, 50, or 60 degreesmeasured at room temperature (about 68°-72° F.).

Steps that may be employed to prepare a spill-resistant border (e.g., atthe edge of a substantially planar surface) can, in one embodiment,include masking areas that are not intended to be modified to behydrophobic/oleophobic, activation of the unmasked areas, reaction witha hydrophobic/oleophobic agent, curing, and unmasking (alternatively,surfaces may be unmasked prior to curing). These steps are outlined inFIG. 2. As will be apparent from the description that follows, the stepsoutlined in that figure are not limiting to the method, and the methodmay be modified in numerous ways that will be apparent to the skilledartisan. For example, surfaces need not be masked where other means ofcontrolling the either activation of the surface or reaction of thesurface with compositions comprising agents that impart hydrophobicityor oleophobicity to a portion of the surface are employed. In addition,surfaces need not be activated where a border can be formed on thesurface in the absence of activation. Moreover, curing may not benecessary for all compositions or agents that impart sufficienthydrophobicity or oleophobicity without curing. Thus, in one embodiment,a method of forming a spill-resistant border may include applying acomposition to a surface that increases the hydrophobicity oroleophobicity of the portion of the surface that will server as aborder, wherein said border forms a perimeter around at least one areathat has a lower hydrophobicity or oleophobicity than the border once itis formed.

The present disclosure provides embodiments of methods for forming aspill-resistant border on a surface that comprise applying a compositionto the surface that increases the hydrophobicity or oleophobicity of aportion of the surface that will serve as a border. One embodimentrelates to the field of nano structures. Such structures when developedin situ on a surface or introduced through a nano featured powdercoating result in a platform for generating selective hydrophobicregions through the monolayer application of fluorosilanes. One silanethat may be used is tridecafluoro-1,1,2,2-tetrahydrooctyltricholorosilane, which functions as a fluorosilane silanizing agent.One approach is called “Polymer Approach.” In this case, a polymer isput into solution in a rapidly evaporating liquid such as acetone orMEK. To this solution a known amount of hydrophobic powder is added (seehydrophobic powder description in the section following differentapproaches). Surfaces prepared by such methods are also provided.

In other embodiments, the present disclosure provides for a surfacecomprising a hydrophobic or oleophobic spill-resistant border, whereinthe border forms a perimeter around at least one area that has a lowerhydrophobicity and/or lower oleophobicity than the spill-resistantborder.

1.0 Surfaces for Forming Spill-Resistant Borders

Spill-resistant borders can be formed on a variety of surfaces, providedthe material that the surface is made from, or a portion thereof, can bemade more hydrophobic and/or more oleophobic. In some embodiments thesurface can be made from a material selected from glass, metal,metalloid, ceramic, wood, plastic, resin, rubber, stone, concrete or acombination thereof. In other embodiments the surface may be made from amaterial selected from the group consisting of glass, ceramic and acombination thereof. In other embodiments, the surfaces may be comprisedof metalloids (e.g., B, Si, Sb, Te and Ge).

Any glass that can be made hydrophobic or oleophobic on a portion of itssurface may be employed as a surface upon which to form aspill-resistant border. Glasses that may be employed as a surfaceinclude, without limitation: soda lime glass, borosilicate glass, sodiumborosilicate glass, aluminosilicate glass, aluminoborosilicate glass,optical glasses, lead crystal glass, fused silica glass, germaniaglasses, germanium selenide glasses, and combinations thereof.

Any metal that can be made more hydrophobic and/or more oleophobic on aportion of its surface may be employed as a surface upon which to form aspill-resistant border. Such metals include without limitation: iron,nickel, chrome, copper, tin, zinc, lead, magnesium, manganese, aluminum,titanium silver, gold, and platinum or combinations thereof, or alloyscomprising those metals. In one embodiment the metal is forming thesurface comprises steel or stainless steel. In another embodiment themetal used for the surface is chromium, is plated with chromium, orcomprises chromium or a chromium containing coating.

Any ceramic that can be made more hydrophobic and/or more oleophobic ona portion of its surface may be employed as a surface upon which to forma spill-resistant border. Such ceramics include, without limitation:earthenware (typically quartz and feldspar), porcelain (e.g., made fromkaolin), bone china, alumina, zirconia, and terracotta. For the purposeof this disclosure a glazing on a ceramic may be considered either as aceramic or a glass.

Any wood that can be made more hydrophobic and/or more oleophobic on aportion of its surface may be employed as a surface upon which to form aspill-resistant border. Such woods include without limitation hard andsoft woods. In some embodiments, woods may be selected from alder,poplar, oak, maple, cherry, apple, walnut, holly, boxwood, mahogany,ebony teak, luan, and elm. In other embodiments woods may be selectedfrom ash, birch, pine, spruce, fir, cedar, and yew. In still otherembodiments the a wood surface may be a composite such as woods productsformed from bamboo, chipped woods, or saw dust and the like.

Any plastic or resin that can be made more hydrophobic and/or moreoleophobic on a portion of its surface may be employed as a surface uponwhich to form a spill-resistant border. Such plastics/resins include,without limitation, polyolefins (such as a polypropylene andpolyethylene), a polyvinylchloride plastics, a polyamides, a polyimides,a polyamideimides, a polyesters, aromatic polyesters, polycarbonates,polystyrenes, polysulfides, polysulfones, polyethersulfones,polyphenylenesulfides, a phenolic resins, polyurethanes, epoxy resins, asilicon resins, acrylonitrile butadiene styrene resins/plastics,methacrylic resins/plastics, acrylate resins, polyacetals, polyphenyleneoxides, polymethylpentenes, melamines, alkyd resins, polyesters orunsaturated polyesters, polybutylene terephthlates, combinationsthereof, and the like.

Any rubber that can be made more hydrophobic and/or more oleophobic on aportion of its surface may be employed as a surface upon which to form aspill-resistant barrier. Such rubbers include, without limitation,styrene-butadiene rubber, butyl rubber, nitrile rubber, chloroprenerubber, polyurethane rubber, silicon rubber and the like.

Any type of stone, concrete, or combination thereof, that can be mademore hydrophobic or more oleophobic on a portion of its surface, may beemployed as a surface upon which to form a spill-resistant border. Insome embodiments, the stone that may be employed as a surface, or acomponent of a surface, is selected from igneous, sedimentary andmetamorphic stone (rock). In one embodiment the stone is selected fromgranite, marble, limestone, hydroxylapatite, quartz, quartzite, obsidianand combinations thereof. Stone may also be used in the form of aconglomerate with other components such as concrete and/or epoxy to forman aggregate that may be used as a surface upon which a spill-resistantborder may be formed (e.g., terrazzo).

2.0 Spill-Resistant Borders

The spill-resistant borders described herein can be formed by causing aportion of a surface to become more hydrophobic and/or more oleophobicby treatment with composition comprising agents that impart thoseproperties to the surface. The hydrophobic/oleophobic properties of thesurface will be affected by both the nature of the surface and the typeof agent that is applied to the surface to form the border.

A spill-resistant border may be placed on a surface so that the borderforms a perimeter around one or more areas that have a lowerhydrophobicity and/or lower oleophobicity than the border, therebyproviding an area within the border that can retain liquids. In otherembodiments, a spill resistant border can be formed on a surface thathas a contact angle with water at room temperature that is less thanabout 10, 15, 20, 30, 40, 50, 60, 70, 80, 90 100, 110, or 120 degrees,and where the surface can be modified to form a border that has acontact angle with water at room temperature that is greater than thecontact angle of water with the surface on which it is formed by about7, 8, 9, 10, 20, 30, 40, 50, or 60 degrees measured at room temperature(about 70-72° F.).

In some embodiments a border may be placed at the edge of a surface, inwhich case it may be referred to as an “edge.” In other embodiments aborder may be placed near an edge of a surface, such as in the form of astrip parallel or substantially parallel to one or more edges of asurface. In some embodiments a border may be placed on a surface at aposition that is not the edge such that the border forms a perimeteraround one or more areas that are have a lower hydrophobicity and/orlower oleophobicity than the border.

Where a border is not placed at the edge it may be termed a “barrier.”Barriers may divide a surface into several regions that have a lowerhydrophobicity and/or lower oleophobicity than the border. Each areahaving a barrier as a perimeter will separately prevent the spreading ofliquid between different areas of the surface. The regions separated bybarriers may be in variety of forms. For example, the regions may be inthe form of a series of concentric circles or a series of regularquadrilaterals (e.g., squares or rectangles, hexagons, or triangles). Insome embodiments a border in the form of an edge, or a border located ator near the edge of the surface, may be employed with borders in theform of barriers. In such an embodiment the surface will not onlyprevent the spread of liquids between regions separated by barriers, butalso prevent or stop liquids from flowing off the surface by blockingpassage of the liquid over the border at the edge. Some examples ofspill-resistant borders, including those with edges and barriers, andcombinations thereof may be seen in FIG. 3.

Spill-resistant borders (including borders in the form of edges andbarriers), regardless of the pattern in which they are formed, aresubstantially 2-dimensional structures. The width of thehydrophobic/oleophobic regions of a surface forming spill-resistantborders can vary depending on the specific application in which theborders are intended to be used. In some embodiments, the borders may befrom about 0.2 to about 2 inches in width, or alternatively, about 0.2,0.25, 0.3, 0.4. 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.25, 1.3 1.4,1.5, 1.75 or 2.0 inches (about 5 mm to 50 mm) in width. In oneembodiment, where the borders are intended for use on food preparationor storage surfaces, (e.g., cutting boards, glass shelving forrefrigerators, or countertops) the borders in the range of 0.2 to 2.0inches. In other embodiments, such as where the spill-resistant bordersare intended for use on food preparation or storage surfaces, theborders can be about 0.4 to 1 inch wide, or alternatively, about, 0.4,0.5, 0.6 0.7 0.75, 0.8, 0.9, or 1.0 inches wide. Border width does nothave to be uniform, and where borders on a surface comprise an edge andbarriers, the edge and barriers may be of different widths or evenvarying widths on the same surface.

Where a combination of a border, such as a border in the form of anedge, and a barrier are used, the hydrophobicity of the barrier and edgemay be controlled such that liquids will be prevented from spreadingbetween different areas of the surface, but the highest resistance toliquid spreading (the highest height of liquid retained) will be at theedge. Thus, in the case of a spill that overflows an area surrounded bya barrier, the spill would flow to an adjacent area, rather than overthe edge.

Spill-resistant borders and barriers may be used to direct liquid towardone or more drains in a surface and can be arranged to channel spilledliquids toward a drain (see e.g., FIG. 3 panels D and E). Borders in theforms of edges and/or barriers may be also combined with drains in asurface so as to direct liquids to a drain or collection site/container.Drains may be in the form of an opening, depression or trough (e.g.,slot, hole, or groove) in the surface bearing the border. Openings,depressions, or troughs may be connected to tubing or pipes that willpermit liquid to be collected or channeled to a desired location (e.g.,a collection container or sewer waste line). Barrier lines that formincomplete perimeters around areas of a surface may also be used tochannel liquids towards a drain (see FIG. 3, Panel D); particularlywhere the barrier lines form a complete perimeter except at the pointwhere they end at or near a drain (see FIG. 3, Panel E). In oneembodiment, one or more drains may be placed at the edge of surface sothat the border forms a continuous perimeter around an area of thesurface up to the point where the drain is located, with the draincompleting the perimeter formed by the border.

For the purpose of this disclosure a border that is not visible is aborder that cannot be readily seen with the unaided human on a clean drysurface using transmitted or reflected light in the spectrum visible tothe human eye. Borders that are not visible may be prepared by treatinga surface with an agent that makes the region forming the borderhydrophobic or oleophobic. If the surface needs to be activated for theapplication of an agent that makes the surface hydrophobic and/oroleophobic, that may be accomplished by chemical etching with agentssuch as HF for brief periods or polishing of the surface with very finepowders such as cerium oxide powder or diamond powders.

For the purpose of this disclosure a border that is visible can be seenwith the unaided human eye on a clean dry surface using transmitted orreflected light in the spectrum visible to the human eye. A border canbe visible but clear, in which case it may, for example, be clear butcolored. A border may also be visible due to surface treatments, such asetching or abrading (e.g., sand blasting or grinding).

A fine visible spill-resistant border, also referred to as a “fineborder”, is a visible border one having fine features on the order of 30to 80 microns, or 40 to 70 microns, or 50 to 60 microns, or about 30,about 40, about 50 or about 60 microns. Fine borders can be prepared,for example, by sand blasting with materials in the range of about 200to about 450 mesh, or 225 to 350 mesh, or 250 to 325 mesh, or materialsabout 200, 250, 300, 350, 400, or 450 mesh (generally metal oxides orcarbide powders).

A coarse visible spill-resistant border, also referred to as a “coarseborder”, is one having features on the order of about 150 to about 250microns, or 175 to about 225 microns, or about 200 microns. Coarsevisible borders can be prepared, for example, by sand blasting withmaterials in the range of about 20 to 60 mesh, or 30 to 50 mesh, or 40to 60 mesh, or materials about 20, 25, 30, 35, 40, 45, 50, 55, or 60mesh.

A medium visible spill-resistant border, also referred to as a “mediumborder”, is a visible border one having features on the order of about80 to about 150 microns, or about 85 to about 140 microns, or about 90to about 120 microns, or about 80, 90, 100, 110, 120, 130, 140 or 150microns. Medium borders can be prepared, for example, by sand blastingwith a mixture of coarse and fine meshed materials (e.g., approximatelyequal amounts by weight, or in the range of a mixture from 1:4 to 4:1 ofcoarse: fine materials by weight). Alternatively, medium borders can beprepared by blasting with materials from about 80 to about 150 mesh, or90 to 145 mesh, 100 to 140 mesh, or about 80, 90, 100, 110, 120, 130,140, or 150 mesh.

Data for fine, medium, and coarse spill-resistant boarders produced bysand blasting glass surfaces appears in Example 17. Fine medium andcoarse borders may also be prepared by etching the surface of glass,ceramics or plastics with chemical etching/activation agents.

2.1 Forming Hydrophobic and Oleophobic Borders on Regions of a Surface

Borders, whether they are visible or not visible, must be morehydrophobic and/or more oleophobic than the regions they surround.Modification of the properties of a surface, or a portion thereof thatserves as a boarder, to impart the desired hydrophobic and/or oleophobicnature can be accomplished by chemical modification. Such modificationscan be accomplished by applying to a surface a composition comprising anagent that increases the hydrophobicity and/or oleophobicity of thesurface upon which it is applied. The result of such chemicalmodification is covalent binding of one or more hydrophobic and/oroleophobic functionalities to the portion of the surface (i.e.modification of the surface) where the border is to be located.

For the purposes of this disclosure a hydrophobic border or surface isone that results in a water droplet forming a surface contact angleexceeding about 45° and less than about 150° at room temperature.Similarly, for the purposes this disclosure a superhydrophobic border orsurface is one that results in a water droplet forming a surface contactangle exceeding about 150° but less than the theoretical maximum contactangle of about 180° at room temperature. Some authors further categorizehydrophobic behavior and employ the term “ultrahydrophobic.” Since forthe purposes of this disclosure, a superhydrophobic surface has contactangles of about 150° to about 180°, superhydrophobic behavior isconsidered to include ultrahydrophobic behavior. Throughout thisdisclosure where a surface (e.g., a border region of a surface) isrecited as being hydrophobic and no specific contact angles are recited,a superhydrophobic surface may also be employed. For the purpose of thisdisclosure hydrophobic shall include superhydrophobic unless statedotherwise.

For the purposes of this disclosure an oleophobic material or surface isone that results in a droplet of light mineral oil forming a surfacecontact angle exceeding about 25° and less than the theoretical maximumcontact angle of about 180° at room temperature.

A variety of methods to increase the hydrophobicity and/or oleophobicityof a surface can be employed. Such methods including the used of one ormore agents, or compositions comprising such agents, that willchemically bind alkyl, fluoroalkyl, or perfluoroalkyl groups to thesurface. Such agents include the use of alkyl, fluroalkyl, orperfluoroalkyl silanizing agents. Other agents that can be used to formhydrophobic or oleophobic borders will depend on the functionalitiesavailable for forming chemical (covalent) linkages to the surfaces. Forexample where surfaces have, or can be modified to have hydroxyl oramino groups, acid anhydrides and acid chlorides of alkyl, fluoroalkyl,or perfluoroalkyl compounds (e.g., the acid chlorides:Cl—C(O)(CH₂)₄₋₁₈CH₃; Cl—C(O)(CH₂)₄₋₁₀(CF₂)₂₋₁₄CF₃; Cl—C(O)(CF₂)₄₋₁₈CF₃or the anhydrides of those acids) can be employed.

2.2 The Use of Silanizing Agents to Apply a Spill-Sesistant Border to aSurface

A variety of silanizing agents can be employed to convert a portion ofthe surface into a spill resistant border. Silanizing agents have bothleaving groups and terminal functionalities. Terminal functionalitiesare groups that are not displaced by reaction with silicate containingglasses (e.g., R groups of compounds of the formula (I)). Leaving groupsare those groups that are displaced from silanizing agents upon reactionwith silicate containing glasses to form bonds with the glass surface.Such silanizing agents include, but are not limited to, compounds of theformula (I):

R_(4-n)Si—X_(n)  (I)

where n is an integer from 1-3;

-   -   each R is independently selected from        -   (i) alkyl or cycloalkyl group optionally substituted one or            more fluorine atoms,        -   (ii) C_(1 to 20) alkyl optionally substituted with one or            more independently selected substituents selected from            fluorine atoms and C₆₋₁₄ aryl groups, which aryl groups are            optionally substituted with one or more independently            selected halo, C_(1 to 10) alkyl, C_(1 to 10) haloalkyl,            C_(1 to 10) alkoxy, or C_(1 to 10) haloalkoxy substituents,        -   (iii) C_(6 to 20) alkyl ether optionally substituted with            one or more substituents independently selected from            fluorine and C₆₋₁₄ aryl groups, which aryl groups are            optionally substituted with one or more independently            selected halo, C_(1 to 10) alkyl, C_(1 to 10) haloalkyl,            C_(1 to 10) alkoxy, or C_(1 to 10) haloalkoxy substituents,        -   (iv) C₆₋₁₄ aryl, optionally substituted with one or more            substituents independently selected from halo or alkoxy, and            haloalkoxy substituents;        -   (v) C_(6 to 20) alkenyl or C_(6 to 20) alkynyl, optionally            substituted with one or more substituents independently            selected from halo, alkoxy, or haloalkoxy; and        -   (vi) —Z—((CF₂)_(q)(CF₃))_(r), wherein Z is a C₁₋₁₂ divalent            alkane radical or a C₂₋₁₂ divalent alkene or alkyne radical,            and q is an integer from 1 to 12, and r is an integer from            1-4;    -   each X is independently selected from —H, —Cl, —I, —Br, —OH,        —OR², —NHR³, or —N(R³)₂;        -   each R² is independently selected C_(1 to 4) alkyl or halo            aklyl group; and        -   each R³ is independently an independently selected H,            C_(1 to 4) alkyl or haloalkyl group.

In one embodiment, R is an alkyl or fluoroalkyl group having from 6 to20 carbon atoms.

In another embodiment, R is an alkyl or fluoroalkyl group having from 8to 20 carbon atoms.

In another embodiment, R is an alkyl or fluoroalkyl group having from 10to 20 carbon atoms.

In another embodiment, R is an alkyl or fluoroalkyl group having from 6to 20 carbon atoms and n is 3

In another embodiment, R is an alkyl or fluoroalkyl group having from 8to 20 carbon atoms and n is 3

In another embodiment, R is an alkyl or fluoroalkyl group having from 10to 20 carbon atoms and n is 3.

In another embodiment, R has the form —Z—((CF₂)_(q)(CF₃))_(r), wherein Zis a C₁₋₁₂ divalent alkane radical or a C₂₋₁₂ divalent alkene or alkyneradical, and q is an integer from 1 to 12, and r is an integer from 1-4.

In any of the previously mentioned embodiments of compounds of formula(I) the value of n may be varied such 1, 2 or 3 terminal functionalitiesare present in compounds of formula (I). In one embodiment, n is 3. Inanother embodiment, n is 2, and in still another embodiment n is 1.

In any of the previously mentioned embodiments of compounds of formula(I), the all halogen atoms present in any one or more R groups arefluorine atoms in some embodiments.

In any of the previously mentioned embodiments of compounds of formula(I), X is independently selected from H, Cl, —OR², —NHR³, —N(R³)₂, orcombinations thereof in some embodiments. In another, embodiment, X maybe selected from Cl, —OR², —NHR³, —N(R³)₂, or combinations thereof. Instill another embodiment, X may be selected from, Cl, —NHR³, —N(R³)₂ orcombinations thereof.

Any border described herein may be formed from one, two, three, four ormore compounds of formula (I) employed alone or in combination toconvert a surface into a hydrophobic or oleophobic surface.

Alkyl as used herein denotes a linear or branched alkyl radical. Alkylgroups may be independently selected from C₁ to C₂₀ alkyl, C₂ to C₂₀alkyl, C₄ to C₂₀ alkyl, C₆ to C₁₈ alkyl, C₆ to C₁₆ alkyl, or C₆ to C₂₀alkyl. Unless otherwise indicated, alkyl does not include cycloalkyl.Cycloalkyl groups may be independently selected from: C₁ to C₂₀ alkylcomprising one or two C₄ to C₈ cycloalkyl functionalities; C₂ to C₂₀alkyl comprising one or two C₄ to C₈ cycloalkyl functionalities;C_(6 to 20) alkyl comprising one or two C₄ to C₈ cycloalkylfunctionalities; C₆ to C₁₈ alkyl comprising one or two C₄ to C₈cycloalkyl functionalities; C₆ to C₁₆ alkyl comprising one or two C₄ toC₈ cycloalkyl functionalities. One or more hydrogen atoms of the alkylgroups found in compounds of formula (I) may be replaced by fluorineatoms.

Haloalkyl as used herein denotes an alkyl group in which some or all ofthe hydrogen atoms present in an alkyl group have been replaced byhalogen atoms. Halogen atoms may be limited to chlorine or fluorineatoms in haloalkyl groups.

Fluoroalkyl as used herein denotes an alkyl group in which some or allof the hydrogen atoms present in an alkyl group have been replaced byfluorine atoms.

Perfluoroalkyl as used herein denotes an alkyl group in which fluorineatoms have been substituted for each hydrogen atom present in the alkylgroup.

In another embodiment, specific compounds that can be employed toprepare spill-resistant borders include compounds that are commerciallyavailable (e.g., from Gelest, Inc., Morrisville, Pa.) including, but notlimited to, those compounds found in the tables of the Examples thataccompany this disclosure such as the compounds in Tables 1 to 9. Somecompounds that may be employed to prepare spill-resistant bordersinclude those that follow, which are identified by their chemical namefollowed by the commercial supplier reference number (e.g., their Gelestreference in parentheses): tridecafluoro-1,1,2,2-tetrahydrooctyl)silane(SIT8173.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane(SIT8174.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane(SIT8175.0); (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane(SIT8176.0);(heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane(SIH5840.5);(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane(SIH5841.7); n-octadecyltrimethoxysilane (SIO6645.0);n-octyltriethoxysilane (SIO6715.0); andnonafluorohexyldimethyl(dimethylamino)silane (SIN6597.4).

Two attributes of silanizing agents that may be considered when forminga spill-resistant border are the leaving group (e.g., X groups ofcompounds of the formula (I)) and the terminal functionality (e.g., Rgroups of compounds of the formula (I)). Silanizing agent leaving groupsdetermine the reactivity of the agent with a substrate. Where, thesubstrate is a silicate glass or stone, the leaving group can bedisplaced to form the Si—O—Si bonds (see Schemes I-VII). The terminalfunctionality determines the level of hydrophobicity that results fromapplication of the silane to the surface.

In addition to assessing the hydrophobicity of a border formed on asurface as a means of assessing its effectiveness for the preparation ofspill-resistant borders, a measurement of the height of water retainedby the border can be employed. In some embodiments the height of waterretained by the borders described herein will be at least 2, 3 4 or 5 mmabove the surface on which the border is formed (measured at roomtemperature). Within such embodiments, the height of water retained bythe borders described herein will be from 2-3.5, or from 2.5 to 4, orfrom 3 to 5, or from 3.25 to 5.25 mm above the surface on which theborder is formed (measured at room temperature).

In order to test the effectiveness of leaving group and terminalfunctionalities of silanizing agents, nine different agents are used toprepare spill-resistant borders on glass plates (see Example 14). Thecontact angles of water with surfaces treated with the agents aresummarized in Table 14. Data for silanizing agents SIT8173, SIT8174,SIT8175, and SIT8176, which have different leaving groups but the sameterminal functional groups, should depend only depend on theeffectiveness of the leaving group. Among those four silanizing agents,the leaving group effectiveness is ranked in the decreasing order aschloro>methoxy>hydro (H)>ethoxy (measured astrichloro>trimethoxy>trihydro>triethoxy). This ranking of the leavinggroups is consistent with their bond dissociation energy.

Bond Dissociation Energies for Various Leaving Groups^(a) BondDissociation Energy, Kcal/mole Me₃Si—NMe₂ (dimethyamine) 98Me₃Si—N(SiMe₃)₂ tris(dimethylamino) 109 Me₃Si—Cl (chloro) 117 Me₃Si—OMe(methoxy) 123 Me₃Si—OEt (ethoxy) 122 ^(a)Data from Gelest, Inc.

Silanes SIH5840.5 and SIH5841.7 contain the(heptadecafluoro-1,1,2,2-tetrahydrodecyl) functional group, however,water-height data suggests the tris(dimethylamino) leaving group, has alower bond dissociation energy than the dimethylamino leaving group.This is also consistent with the bond dissociation energies given above.

2.3 Effect of Terminal Groups on Liquid Retention by Spill-ResistantBorders

The choice of hydrophobic or oleophobic agents, particularly theterminal groups of silane reagents, influences a border's ability toretain various liquids. Alkyl functionalities, and particularly alkyterminal functional functionalities of silanizing agents, while suitablefor use in the preparation of borders, generally are not as effective astheir fluorinated or perfluorinated counterparts at retaining aqueousliquids based on the height of water the borders can retain. Compare thedata in Examples 5-7 with Examples 8 and 9.

In addition to the ability to retain aqueous based solutions,suspension, and emulsions, embodiments of the borders disclosed hereintend to have oleophobic behavior, permitting them to retain oils. Thisis particularly true where the borders have been prepared withsilanizing agents having fluorinated or perfluorinated alkyl groups(e.g., where the terminal functionality of a silane of the formulaR_(4-n)Si—X_(n) is a fluorinated alkyl or perfluoroalkyl). See, forexample, the contact angle data in Example 14 and Table 14, for mineraloil and borders comprising fluorinated alkanes. The height of mineraloil that can be retained by boarders comprising fluorinated alkyl groupsis exemplified in Example 15, in which data for two fluoroalkylsilanizing agent treatments and mineral oil is presented.

2.4 Use of Compounds Other than Silanizing Agents to FormSpill-Resistant Borders

Other agents that can be used to form hydrophobic or oleophobic borderswill depend on the functionalities available for forming chemical(covalent) linkages between hydrophobic/oleophobic component and thesurfaces. For example where surfaces have, or can be modified to have,hydroxyl or amino groups then acid anhydrides and acid chlorides ofalkyl, fluoroalkyl, and perfluoroalkyl compounds may be employed (e.g.,the acid chlorides: Cl—C(O)(CH₂)₄₋₁₈CH₃; Cl—C(O)(CH₂)₄₋₁₀(CF₂)₂₋₁₄CF₃;Cl—C(O)(CF₂)₄₋₁₈CF₃ or the anhydrides of those acids) can be employed.

3.0 Surface Activation

Surfaces may benefit from, or even require, activation to effectivelyreact with agents that will increase the hydrophobicity and/oroleophobicity of the surface. Where surfaces do not comprise a suitabletype or suitable number of functionalities for reaction withcompositions comprising agents that will increase the hydrophobicityand/or oleophobicity of the surfaces, they may be activated to changethe surface properties

Where a surface does not contain a suitable type of functional group, orsufficient numbers of those functional groups, to permit effectiveincreases in hydrophobicity an/or oleophobicity, the surface can bereacted with reagents that will modify the surface so as to introduce asufficient numbers of suitable functionalities. Alternatively, wheredesired functional groups on a surface are blocked or otherwiseunavailable, the surface may be activated by various physical orchemical treatments.

3.1 Activation of Glass and Ceramic Surfaces

In one embodiment, where a surface is a silicate containing glass orceramic having less than a desirable number of functional groups forreaction with silanizing agents (e.g., alkylsilyl chlorides orperfluoroalkylsilyl chlorides, or more generally compounds of formula(I), that can covalently bind hydrophobic and/or oleophobicfunctionalities to the surface), the surface can be activated bychemical or physical means. Activation of SiO₂ containing glasses(silicate glasses or silicate containing glasses) is considered torequire exposure of SiO₂ (e.g., Si—OH groups) on the glass surface. Someglass compositions that contain SiO₂, along with glasses that do not,are recited in the table that follows. A skilled artisan will appreciatethat ceramics and glasses that do not comprise SiO₂ may be activated forreaction with agents that result in converting the portion of a surfacethat is to serve as a border into a hydrophobic or oleophobic surfaceusing the methods described for silicate glasses or similar methods.

Chemical Composition and Physical Properties of Some GlassesBorosilicate (low expansion, Glass Wool (for Special optical Soda-limeglass similar to Pyrex, thermal glass (similar to Germanium Properties(for containers) Duran) insulation) Lead crystal) Fused silica Germaniaglass selenide glass Chemical 74 SiO₂, 13 81 SiO₂, 12.5 63 SiO₂, 16 41.2SiO₂, SiO₂ GeO₂ GeSe₂ composition, Na₂O, 10.5 B₂O₃, 4 Na₂O, Na₂O, 8 34.1PbO, wt %, CaO, 1.3 2.2 Al₂O₃, CaO, 3.3 12.4 BaO, Al₂O₃, 0.3 0.02 CaO,B₂O₃, 5 6.3 ZnO, K₂O, 0.2 SO₃, 0.06 K₂O Al₂O₃, 3.5 3.0 K₂O, 0.2 MgO,MgO, 0.8 2.5 CaO, 0.01 TiO2, K₂O, 0.3 0.35 Sb₂O₃, 0.04 Fe₂O₃ Fe₂O₃, 0.20.2 As₂O₃ SO₃ Viscosity 550-1450° C.: 550-1450° C.: 550-1400° C.:500-690° C.: 1140-2320° C.: 515-1540° C.: log(η, Pa · s) = A + A =−2.309 A = −2.834 A = −2.323 A = −35.59 A = −7.766 A = −11.044 B/(T in °C.-T_(o)) B = 3922 B = 6668 B = 3232 B = 60930 B = 27913 B = 30979 T_(o)= 291 T_(o) = 108 To = 318 T_(o) = −741 T_(o) = −271.7 T_(o) = −837Glass transition 573 536  551 ~540 1140 526 ±  395^([30]   )temperature, T_(g), 27^([27][28][29]) ° C. Coefficient of 9   3.5 10 70.55 7.3 thermal expansion, ppm/K, ~100-300° C. Density 2.52    2.2352.550 3.86 2.203 3.65^([31]) 4.16^([30]) at 20° C., [g/cm³], ×1000 toget [kg/m³] Refractive index 1.518    1.473 1.531 1.650 1.459 1.6081.7     n_(D) ^(]) at 20° C. Dispersion at 86.7   72.3 89.5 169 67.8 14620° C., 10⁴ × (n_(F) − n_(C)) Young's modulus 72 65 75 67 72 43.3^([33])at 20° C., GPa Shear modulus 29.8   28.2 26.8 31.3 at 20° C., GPaLiquidus 1040  1070^([34]) 1715 1115 temperature, ° C. Heat capacity at49 50 50 51 44 52 20° C., J/(mol · K) Surface tension, 315 370  290 at~1300° C., mJ/m²

Some of the potential interactions of silicate containing substrates(e.g., many glasses) with compounds of formula (I) having hydrogen,halogens (illustrated by chlorine), —O-alkyl, or —N(alkyl)₂ substituentsas leaving groups are illustrated in Schemes I-VII.

Reaction Mechanism: Hydrolytic deposition of silane. The reaction ofwater with the corresponding silane results in the loss of threeequivalents H₂ gas producing a triol-silane, followed by polymerizationand reactivity With the substate producing hydrogen bonding that resultsin net silica-oxygen bond formation.

Reaction Mechanism: Hydrolytic deposition of silane. The reaction of Water with the corresponding trichloro-silane results in the loss ofthree equivalents of hydrogen chloride producing a triol-silane,followed by polymerization and reactivity with the substate producinghydrogen bonding that results in net silica-oxygen bond formation.

Reaction Mechanism: Hydrolytic deposition of silane. The reaction ofwater with the corresponding triethoxy-silane results in the loss ofthree equivalents of ethanol producing a triol-silane, followed bypolymerization and reactivity with the substate producing hydrogenbonding that results in net silica-oxygen bond formation.

Reaction Mechanism: Anhydrous Deposition of Silan. Higher temperaturesand extended reaction times must occur for the reaction to occur at highyield. The reaction of alcohol substrate with the correspondingamino-silane results in the loss of dimethylamine and silica-oxygenbonding.

Reaction Mechanism: Hydrolytic deposition of silane. The reaction ofwater with the corresponding triamino-silane results in the loss ofthree equivalents of dimethylamine producing a triol-silane, followed bypolymerization and reactivity with the substrate producing hydrogenbonding that result in net silica-oxygen bond formation producinghydrophobicity.

Reaction Mechanism: Hydrolytic deposition of silane. The reaction ofwater with the corresponding, trimethoxy-silane results in the loss ofthree equivalents of methanol producing a triol-silane, followed bypolymerization and reactivity with the substate producing hydrogenbonding that results in net silica-oxygen bond formation.

Reaction Mechanism: Anhydrous Deposition of Silane. Higher temperaturesand extended reaction times must occur for the reaction to occur at highyield. The reaction of alcohol substrate with the correspondingamino-silane results in the loss of dimethylamine and silica-oxygenbonding.

Chemical means that can be used to activate and/or etch a surface andparticularly glass or ceramic surfaces, include without limitation,reaction with: acids (e.g., hydrofluoric acid); base (e.g., 1 to 10 NNaOH or KOH with or without added sodium or potassium silicate); sodiumor potassium silicate; or fluorine containing salts (e.g., a compositioncomprising ammonium fluoride). A variety of commercial etching agentsthat can be used to activate glass and/or ceramic surfaces are alsoavailable, including, but not limited to, “New Improved Armour Etch”(Armour Products, Hawthorn, N.J.), with GALLERY GLASS® etching medium(Plaid Enterprises, Inc., Norcross, Ga.), Professional 30 second GlassEtching Cream (Martronic Corp, Salkum, Wash.), ETCHALL® Etching Cream (B& B Products, Inc., Peoria, Ariz.), and VTX catalyst (Advanced OxidationTechnology, Inc.) in the presence of hydrogen peroxide.

The pH of activating agents/etchants used to treat glass/ceramicsurfaces can vary widely. The activating agents/etchants listed inExample 5 and Table 5 varied in their pH from 1 to 14. As noted inExamples 1-5, and Tables 1-5, many of the compositions employed forglass etching are acidic with a pH of ˜3, one is basic with a pH of 9,and sodium silicate and sodium hydroxide solutions are significantlymore basic. The height of water retained on glass plates bearingspill-resistant borders formed with Gelest silane SIT8174 is plotted asa function of pH of the activating agent/etchant employed in FIG. 4.,which indicates that the height of water retained on the plates isbasically independent of pH.

In one embodiment activation of glass by exposure of SiO₂, (Si—OHgroups), 1 which can react with silanizing agents and the like, iscarried out by chemical treatment with 5% HF, 1 or 10 N NaOH, sodiumsilicate, or VTX in the presence of peroxide.

In one embodiment, activation and/or etching of glass or ceramic isconducted with HF. In another embodiment, activation of glass and orceramic surfaces is conducted by treatment of the surface withcommercial etching compositions comprising a fluoride salt.

Some of the reactions that SiO₂ containing glasses undergo with HF arelisted below.

SiO₂(S)+4HF(aqueous(aq))→SiF₄(g)+2H₂O(l)  (Equation (1a))

SiO₂(S)+6HF(aq)→H₂SiF₆(aq)+2H₂O(l)  (Equation (1b))

The SiO₂ in the glass can be dissolved by both reactions (1a) and (1b).

In another embodiment, activation and/or etching of SiO₂ containingglasses is conducted with ammonium bifluoride, such as in some acidicetching creams. Some of SiO₂ containing glass undergoes with ammoniumbifluoride, potassium fluoride, and sodium fluoride, are listed below.

SiO₂+4[NH₄][HF₂]→SiF₄+4[NH₄]F+2H₂O  (Equation (2a))

SiO₂+4[K][HF₂]→SiF₄+4[K]F+2H₂O  (Equation (2b))

SiO₂+4[Na][HF₂]→SiF₄+4[Na]F+2H₂O  (Equation (2c))

In yet other embodiments, activation and/or etching of SiO₂ containingglasses is conducted with sodium hydroxide or sodium silicate, whichalso attack SiO₂ and possible reactions with the glass include:

(X) SiO₂ glass+2NaOH→Na₂SiO₃+H₂O+Etched glass  (Equation (3))

(X) SiO₂ (glass)+Na₂SiO₃ (water glass)→Na₂SiO₃ (water glass with higherSiO₂ content)  (Equation (4))

where X in Equations (3) and (4) represents a non-SiO₂ part of theglass.

In general, the aqueous etchants such as HF, NaOH, Na₂SiO₃, and VTXproduced clear borders that are not visible. Etching creams thatcontained ammonium bifluoride with large quantities of inactiveingredients generally produce translucent or visible borders. Only oneof the etching creams with a pH of 9 (Gallery Glass Window Etch)produces a clear border. That etching cream is liquid with minimumamounts of inactive ingredients. Without wishing to be bound by theory,it appears that translucent or visible borders produced by etchingcreams are caused by the presence of inert ingredients masking thesurface which causes the etching reaction to take a longer time and alsomakes it irregular and translucent. The absence of inactive ingredientsin pure aqueous solution causes them to produce a more uniform etching,which leaves the etched surface transparent or clear Attempts to employinactive materials, such as 512 polymer particles, with 5% HF to producea patterned border due to masking of the glass by the polymer particlesis, however, ineffective as the 512 powder does not produce anysignificant masking effect.

Glasses and ceramics may also be abraded to improve their reaction withagents such as the silanizing agents of formula (I). Mechanical abrasionmay be conducted using a variety of techniques known in the art,including but not limited to abrading or blasting (sand blasting) withhard particles such as SiC, SiO₂, or Al₂O₃. The particle sizes can becoarse (e.g., 30-50 mesh) to cause a coarse appearance, or fine (e.g.300 mesh) to obtain a fine appearance, or medium (e.g., a blend of 30-50and 300-400 mesh) to obtain a surfaces with an appearance that isintermediate between fine and coarse. Abrasion may also be conductedusing immobilized particles of hard materials in the form of sheets(e.g., sand paper or emery cloth) or aggregated hard particles in theform of grinding equipment (e.g., grinding stones an the like).

Without wishing to be bound by any theory, abrading processes arethought to activate SiO₂ containing glasses and ceramics by removingrelatively more of softer non-SiO₂ components than the hard SiO₂components of glass and ceramic compositions. Thus, SiO₂ sites (e.g.,existing as groups comprising Si—OH functionalities), which can reactwith silanizing agents, are preferentially exposed. Because ofsignificant roughness, a boarder produced by abrasion is generallytranslucent or visible.

In contrast to abrasion with moderately large particles, where theparticles of abrading agent are very fine (e.g., 1,200 grit or 15microns to 200,000 grit 0.125 microns) they may serve as a polishingagent, and still produce activation of a glass or ceramic surface. Thus,in one embodiment, polishing agents such as cerium oxide, tin oxide,iron oxide, silicon dioxide, chromium oxide, aluminum oxide, or diamondpowders, having a size from about 1,200 mesh to about 200,000 mesh, ormore typically from 50,000 to 200,000 mesh can be used to polish andactivate ceramic and glass surfaces for the preparation ofspill-resistant borders that are not visible. In some embodiments, thepolishing powders can have a mesh (grit) size of about, 1,000, 2,000,3,000, 4,000, 8,000, 12,000, 16,000, 20,000, 40,000, 50,000, 100,000 or200,000 grit.

Polishing with fine particles, such as cerium oxide particles, is oftenconducted in slurry form using a motorized wheel. Data for the effect ofcerium oxide polishing and its effect on the height of water retained byspill-resistant borders on glass surfaces is found Example 10.

In some embodiments, a combination of chemical treatments or acombination of mechanical (physical treatments such as abrasion orpolishing) and chemical treatments may be employed to activate surfaces(e.g., glasses and ceramics) on which spill-resistant borders are to beformed. Combining of treatments for surface activation do notnecessarily produce the highest water retention on glass or ceramicplates. Treatment of plates with sodium silicate after sandblasting withcoarse particles or fine particles resulted in spill-resistant bordershaving lower water height retention as can be noted from Table 5. Thissuggests that sodium silicate treatment can inactivate some of the sitesto which silanizing agents might otherwise have attached. In addition,the data in Table 5 indicates that NaOH etching of borders prepared bysandblasting produced even a larger reduction of the water heightcapacity than sodium silicate treatment.

While many chemical treatments are suitable for the activation ofsurfaces and have the ability to markedly increase the ability ofspill-resistant borders formed on those surfaces to retain liquids, theuse of chemical treatments often entails the use of materials that aretoxic, caustic or corrosive, particularly where glass, stone, orceramics are treated. In contrast, physical treatments, such as abrasionby sand blasting or polishing, tend to utilize or produce fewer noxious,toxic, caustic or corrosive chemicals; hence, the materials used andby-products produced are less likely to have the same degree ofenvironmental impact as caustic etchants.

3.23 Activation of Non-Glass and Non-Ceramic Surfaces

Activation of Metals: Metals and alloys can be activated by manydifferent methods.

-   -   1. Blasting the surface with hard particles. The hard particles        include oxides (SiO₂, Al₂O₃, ZrO₂, etc.), carbides (SiC, WC,        etc.), steel shot, glass shot, etc.    -   2. Etching of surfaces with chemical reagents. All metals can be        etched to reveal the grain boundaries and the grain interiors.        By controlling the chemical concentration and exposure time, the        grain interiors can be etched to create active sites for binding        with silanes. The chemicals used include acids, alkalis, and        salts.    -   3. Anodizing is another process used to activate metal surfaces.        In this process, the metal or alloy to be activated is made an        anode in an electrolytic bath containing acid. When a current is        applied, the anode surface is oxidized with micron to nano size        features. The anodizing process is most commonly used for        aluminum but can also be applied to other metals and alloys.        Titanium is another common material that is anodized.    -   4. Combined blasting and etching is another method for        activating metals. Blasting creates the regions of high and low        stresses and etching preferentially etches the high stress areas        to create the desired micron/nano size features. The final size        is controlled by the particle size and hardness of the blast        media used, choice of an etchant, and etching time. Sometimes        temperature is used to enhance the etching process.    -   5. Wood is porous and generally does not require activation,        where binding if agents such as silanes will be to groups such        as hydroxyl, that are already present in the cellulose. Its        porous surface and body can also be impregnate with chemicals        such as SiCl₄, Si(OEt)₄, or Si(OMe)₄, or Si(OR)₃Cl for creating        Si—OH sites to which silanes attach to create covalent Si—O—Si        bonds.    -   6. Plastics can also be chemically bonded to silanes. In some        cases, plastics may be inert to bonding with agents that will        impart a hydrophobic or oleophobic characteristic to a portion        of the surface. Surface activation to bond to silanes requires        creating active sites in the plastic molecules, which can        generally be done by exposure to thermal plasma generated using        electrical discharge methods. In certain circumstances, chemical        treatments may also be used for plastic activation. In one        instance, PVC can be activated by treating its surface with a        solvent use as a PVC cleaner such as MEK.

4.0 Control of Spill-Resistant Border Dimensions, Placement andShape—Masked and Non-Masked Border Formation.

The shape, dimensions and placement of spill-resistant border onsurfaces can be controlled by a variety of means that broadly fall intotwo categories, control of the activation process and control of portionof a surface exposed to compositions comprising agents that willincrease the hydrophobicity and/or oleophobicity of the portion of thesurface that will form the border (e.g., silanizing agents such ascompounds of formula I). Control of the activation process and the localplacement of compositions comprising agents can be used alone or incombination.

Masks can control chemical, physical (e.g., abrasion, sandblasting,polishing) or photochemical activation of surfaces. The choice ofmasking agents will depend on the treatments that the mask is expectedto control. For example, where activation of a surface and/or theapplication of silanizing agent will not involve mechanical treatmentssuch as abrasion or sand blasting, waxes can be used as a masking agent.Alternatively, where sand blasting is used activate and/or etch asurface, a more durable masking agent, such as a rigid or flexibleplastic, resin, or rubber/rubberized material may be more desirable.Masking may be attached to the surface through the use of adhesives,which may be applied to the masking agent, the surface, or both. In oneembodiment, the mask may formed from a photo sensitive agent such as aphoto resist that upon exposure to light can be removed to expose theglass surface (see e.g., U.S. Pat. No. 4,415,405). Where masks are to besubject to chemical treatments in an etching and/or activation process,or chemical treatments involved in the application of compositions thatmodify hydrophobic/oleophobic properties of a surface, the mask shouldbe resistant to the reagents employed in those processes.

More than one type of mask can be used in the process of preparing itemswith spill-resistant borders. For example, one type of mask may beemployed for control of activation/etching and another type of mask tocontrol the application of composition comprising agents that increasethe hydrophobic or oleophobic properties of a surface.

Masks need not be in direct contact with a surface for all types oftreatments. For example, where glass is subject to photochemical etchingwith ultraviolet light or ultraviolet light and heat, the mask need onlycontrol the regions where light falls on the surfaces (i.e., the mask isa photomask, see e.g., U.S. Pat. No. 5,840,201 or 6,136,210)Alternatively, a combination of a photoresistive coating as a mask tocreate pattern, and a chemical etchant can be employed to activate/etchglasses, ceramics, and other materials in specific regions where bordersare to be formed.

As an alternative to the use of masks, it is possible control thelocation of border formation by limiting the portion of a surface towhich activation/etching agents, and/or compositions comprising agentsthat will increase the hydrophobicity or oleophobicity of a surface willbe applied. In one embodiment, activation or etching is carried out witha chemical composition that does not flow significantly from the area towhich it is applied under the conditions employed (e.g., the etchant isa cream or paste), thereby permitting activation of portion of a surfacethat will form a border without the use of a mask. In anotherembodiment, sandblasting can be conducted using equipment which producesa narrowed stream of particles permitting local abrasion of a surfacewithout a mask (using such techniques the borders may have more diffuseedges). In still another embodiment, compositions comprising agents thatwill increase the hydrophobicity and/or oleophobicity of a surface maybe applied to limited regions (e.g., by the painting, printing, orstamping of silanizing agents on a portion of a surface). In oneembodiment, or the use of applicators such as foams or spongy materialformed in the shape of the border desired are employed. Thus, it ispossible to prepare spill-resistant borders on surfaces omitting stepswhere masks are used.

5.0 Retention of Liquids by Spill-Resistant Borders

The spill-resistant borders described herein can prevent a large varietyof liquids from moving beyond the borders edge until the height of theliquid exceeds a critical level. Included in the liquids that can beretained by the spill-resistant borders described herein are water, andaqueous liquids, aqueous suspension, and aqueous emulsions. In addition,alcohols, and aqueous alcohol mixtures (e.g. wines and distilled alcoholcontaining liquids such as vodka) can be retained by the spill-resistantborders described herein. Non-aqueous materials including many oils andlipids can be retained by spill-resistant borders, particularly wherethe border is comprised of one or more types of fluorinated orperfluorinated alkane, alkene, or aryl groups (an alkyl group where allhydrogen atoms are replaced by fluorine atoms), or formed from one ormore highly fluorinated alkanes, alkenes, alkynes or aryl group wheregreater than about 65%, 75%, 80%, 85% 90%, 95%, or 98% of the hydrogenatoms are replaced by fluorine atoms. In one embodiment, spill-resistantborders formed with agents (e.g., silanizing agents) comprising one ormore perfluorinated alkane groups or highly fluorinated alkane groupsare useful not only for preventing the spilling of aqueous materials,but also for non-aqueous materials, including alcohols, aqueous alcoholcombinations, and many oils and lipids.

In some embodiments, the height of water retained by the bordersdescribed herein is about 2 to about 3.5, or about 2.5 to about 4, orabout 3 to about 5, or about 3.5 to about 5.25 millimeters (mm).Alternatively, the height of water retained by spill-resistant bordersabove the surface on which the border is formed (measured at roomtemperature) is be about 2.0, 2.25, 2.5, 2.75, 3.0, 3.25, 3.5, 3.75,4.0, 4.25, 4.5, 4.75, 5.0, 5.25 or 5.5 millimeters. In some embodimentsthe spill-resistant borders provide a contact angle of: about 45° toabout 125°; about 50° to about 110°; about 50° to about 90°; about 90°to about 125°; or about 75° to about 115° with water on a glass surfacethat has a fine, medium or coarse visible border. In other embodimentsthe spill-resistant borders provide a contact angle of: about 60° toabout 116°; about 65° to about 90°; about 90° to about 116°; or about70° to about 115° with water on a glass surface that has a border thatis not visible.

Reduced temperatures do not prevent the spill-resistant bordersdescribed in this disclosure from retaining liquids. The performance ofseveral, spill-resistant borders formed on glass at surface attemperatures typically employed in food refrigeration is depicted inExample 12. The height of ice cold water (about 0°-4° C. or about 32° to39° F.) retained by the spill-resistant borders described herein isgenerally about 5% less than that observed with room temperature water.

Non-aqueous liquids that can be retained by the spill-resistant bordersdescribed in this disclosure include alcohols, liquid comprising analcohol, a liquid comprising alcohol and water, oils such as mineraloil, lipids (e.g., triglycerides, fatty acids or their esters).Combinations of aqueous and non-aqueous liquids, even where immiscible,can also be retained by the spill-resistant-borders described herein.

As depicted in Example 11, the spill-resistant borders described hereincan retain alcohol containing liquids, (e.g., a liquid comprising analcohol, or a liquid comprising alcohol and water). In some embodiments,the height of those liquids retained by the spill-resistant bordersdescribed herein is about 1 to about 4.25 mm, or about 1.5 to about 4.2mm, or about 2.0 to about 4.1, or about 2.5 to about 4.1 mm, above thesurface of on which the border is formed. Alternatively, the height ofthose liquids (e.g., wine or distilled liquors such as vodka) retainedby spill-resistant borders above the surface on which the border isformed (measured at room temperature) can be about 0.8, 0.9, 1.0, 1.2,1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.75,3.0, 3.25, 3.5, 3.75, 4.0, or 4.25 millimeters.

As can be observed from the data in Example 14, the contact angle ofwater with a hydrophobic and/or oleophobic surface is generally higherthan the contact angle of mineral oil with that surface. The contactangle for water and silane treated surfaces/borders is typically 3 to 6time higher than for control, untreated sample surfaces. In contrast,the contact angle for mineral oil and silane treated borders istypically 2 to 9 times higher than control, untreated sample surfaces.The data in Examples 14 and 15 indicate that silanizing agents thatproduce the highest contact angles for water also produce the highestcontact angles for mineral oil, indicating that the higher thehydrophobicity of the border formed by the silane treatment, the betterits performance will be in retaining water and oils. The data in thoseexamples also indicate that trichlorinated silanizing agents(trichlorosilanes, e.g., compounds of formula (I) where n is 3 and X isCl) produce the highest contact angles for both water and mineral oil.

Examples 14 and 15, indicate that the borders formed with fluorinatedalkyl silanes SIT8174 and SIT5841.7 each produce mineral oil heightsexceeding 1.9 mm, regardless of the treatment used to activate thesurface prior to their deposition. This contrasts with thenon-fluorinated alkyl silane SI06715.0, which produces mineral oilheights of about 1 mm. This suggest that the higher contact anglesobserved for SIT8174 and SIT5841.7 correlate with higher mineral oilheights and spill-resistance observed for borders formed with thoseagents. The data further indicate a correlation between the terminalfunctionalities' fluorine content (e.g., the R groups of a compound offormula (I)) and their ability to serve as oleophobic spill-resistantborders that retain lipid/oils.

In some embodiments, the height of oils (e.g., light mineral oil)retained by the borders described herein is about 0.8 to about 2.5 mm,or about 0.9 to about 2.4 mm, or about 1.0 to about 2.4 mm, or about 1.5to about 2.5 mm, or about 1.9 to 2.4 mm. Alternatively, the height ofoils (e.g., mineral oil) retained by spill-resistant borders above thesurface on which the border is formed (measured at room temperature) canbe about 0.8, 0.9, 1.0, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0,2.1, 2.2, 2.3, 2.4, or 2.5 millimeters. In some embodiments thespill-resistant borders provide a contact angle of: about 36° to about91°; about 40° to about 70°; about 70° to about 90°; about 45° to about85°; or about 50° to about 80° with oil (e.g., light mineral oil) on aglass surface that has a fine, medium or coarse visible border. In otherembodiments the spill-resistant borders provide a contact angle of:about 27° to about 109°; about 30° to about 105°; about 40° to about105°; about 40° to about 75°; about 75° to about 109°; or about 80° toabout 100° with oil (e.g., light mineral oil) on a glass surface thathas a border that is not visible.

6.0 Effects of Surface Cleaning and Use on the Ability to Retain Liquids

Spill-resistant borders by their nature are exposed not only to theliquids spilled, but also to agents used to clear the surface after aspill. In addition, surfaces bearing spill-resistant borders are subjectto wear from contact between items and the surface. Exposure to adiversity of liquids and wear can be exemplified by the use ofspill-resistant borders on shelving for refrigerated enclosures for foodstorage. Refrigeration unit shelves in both commercial and home settingsare subject to both frequent use and cleaning after exposure to avariety of spilled foods and food preparation materials. Thespill-resistant borders described herein are durable and retain theirability to prevent the spread of spilled materials even after cleaningwith detergent solutions and after significant contact with items thatcan cause ware on the surface.

Example 15 demonstrates the ability of spill-resistant borders on glasssurfaces to retain a variety of food items after exposure to a varietyof food items followed by cleaning after each exposure. In addition,that example demonstrates the ability of the spill-resistant borders toretain water (cooled) even after repeated cleaning.

The type of ware/abrasion that would result from the typical use ofspill-resistant borders on shelving in home or commercial refrigeratedenclosures can be simulated. A test of spill-resistant borders subjectto repeated abrasion by a glass jar to simulate ware shows the borders,and particularly coarse visible boarders, can withstand repeatedabrasion. See Example 13 and Tables 13A and 13B. The high abrasionresistance of these borders is likely the result of covalently bondednet works of Si—O—Si bonds formed in the interaction of the glasssurface and silanizing agents. Overall, the spill-proof bordersdescribed herein are highly durable for expected use in refrigeratorsand in other applications.

EXAMPLES Example 1 A Spill-Resistant Border Formed at the Edge of GlassPlates Employing Hydrofluoric Acid Activation

Glass plates (4-inch by 4-inch squares) are used to demonstrate borderformation and to measure the border's water-holding capacity (height ofwater retained). Borders are a 0.5-inches wide hydrophobic and/oroleophobic regions applied to the outside edge of the glass plates. Thecenter part of the glass that is not to be treated is masked with anadhesive plastic film (e.g., vinyl electrical tape). After masking,glass plates are activated by etching with a 5% solution of HF,typically for 30 seconds. After etching plates are washed thoroughlywith water, excess water blown away with a stream of air, and the platesare dried in a 200° F. oven for 5 min. After cooling, a solution of theindicated silanizing agent in hexanes (1% silane by weight) is appliedto the border area. After the hexanes have evaporate, plates are curedat 200° F. for 15 minutes, the plates are cooled, and the mask isremoved. The appearance of the border region remained the same as theoriginal plate after HF etching, silane application, and curing.

Plates prepared as described above are placed on a level surface, andthe water-retention level of each plate is measured by filling the areawithin the border (the previously masked area) with water. Water isadded to center of each plate until border breakage (water overflowingthe border) is noted. The volume of water added to the center of a plateis divided by the area within the border of that plate to derive theheight of the water retained by the plate. The appearance of the border,the name and molecular formula of the silane used to treat the plate,and the height of the retained water are summarized in Table 1 andplotted in the graph shown in FIG. 1. Although the pH of the etchingsolution is listed in Table 1 as “1”, the value of the pH can be lessthan 1 depending on a number of factors including the temperature.

TABLE 1 5% HF and Five Different Silanes* Water Border Molecular HeightEtchant pH Appearance Silane Formula (mm) 5% HF 1 Clear SIT 8174C₈H₄Cl₃F₁₃Si 4.69 (Tridecafluoro-1,1,2,2 Tetrahydrooctyl)Trichlorosilane 1 Clear SIN 6597.4 C₁₀H₁₆F₉NSi 3.50Nonafluorohexyldimethyl (dimethylamino)silane 1 Clear SIH 5840.5C₁₄H₁₆F₁₇NSi 4.30 Heptadecafluorotetrahydrodecyidimethyl(dimethylamino)silane 1 Clear SIH 5841.7 C₁₆H₂₂F₁₇N₃Si 4.65Heptadecafluoro-1,1,2,2 Tetrahydrodecyltris (dimethylamino) silane 1Clear SIT 8173 C₈H₇F₁₃Si 3.91 Tridecafluoro-1,1,2,2Tetrahydrooctylsilane *The silanes employed are procured from Gelest,Inc., whose product numbers are also given as an additional reference.

The brief etching with 5% HF and treatment with the indicted silanesproduce a clear border that is not visible. While each of the silanizingagents listed produce a spill-resistant border,tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane (SIT8174), andheptadecafluoro-1,1,2,2-tetrahydrodecyltris(dimethylamino)silane(S1115841.7) retain water approximately equally well, andheptadecafluorotetrahydrodecylimethyl (dimethylamino)silane (SIH5840.5)retains water a level that is nearly as high.

Example 2 Spill-Resistant Border Formation Employing Sodium SilicateAcid Activation

Seven 4 inch×4-inch glass plates are prepared as in Example 1, exceptthat the plates are etched with an aqueous sodium silicate solution(SiO₂/Na₂O ratio 3.22, with 8.9% Na₂O and 28.7% SiO₂ by weight) for 2minutes and 30 seconds in place of HF etching. The etched borders aretreated with one of the seven different silanes listed in Table 2, andthe plates are cured at 200° F. for 15-30 min. The tape mask is removedfrom the plates and height of water retained by the silanized borders ismeasured. Data from the plates is summarized in Table 2. Sodiumsilicate, like the 5% HF etch employed in Example 1, produces a clearborder. Again, tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane(SIT8174), andheptadecafluoro-1,1,2,2-tetrahydrodecyltris(dimethylamino)silane(SIH5841.7) retain greater than 4.5 mm of water.

TABLE 2 Sodium Silicate Etch and Seven Different Silanes Water BorderMolecular Height Etchant pH Appearance Silane Formula (mm) Sodium 12.5Clear SIT 8174 C₈H₄Cl₃F₁₃Si 4.50 SilicateTridecafluoro-1,1,2,2-Tetrahydrooctyl Trichlorosilane 12.5 Clear SIO6645 C₂₁H₄₆O₃Si₃ 3.96 n-Octadecyl Trimethoxysilane 12.5 Clear SIO 6715C₁₄H₃₂O₃Si₃ 3.48 n-Octyl Triethoxysilane 12.5 Clear Sin 6597.4C₁₀H₁₆F₉NSi 3.34 Nonafluorohexyldimethyl (dimethylamino) silane 12.5Clear SIH 5840.5 C₁₄H₁₆F₁₇NSi 3.74Heptadecafluorotetrahydrodecyldimethyl (dimethylamino) silane 12.5 ClearSIH 5841.7 C₁₆H₂₂F₁₇N₃Si 4.50 Heptadecafluoro-1,1,2,2,-Tetrahydrodecyltris (dimethylamino) silane 12.5 Clear SIT 8173 C₈H₇F₁₃Si3.65 Tridecafluoro-1,1,2,2-Tetrahydrooctyl silane

Example 3 A Coarse Visible Spill-Resistant Border Formed at the Edge ofGlass Plates Employing Sand Blasting as a Means to Activate the GlassSurface

Nine 4 inch by 4-inch glass plates with the center masked withelectrical tape as in Example 1 are sandblasted using coarse grit sand(43 mesh) to form a coarse visible border. The blasted surface is washedwith water, dried, and silanated by applying one of nine differentsilanizing agents to the etched border of each plate. The silanatedplates are cured at 200° F. for 15-30 min. After cooling, the mask isremoved and the plates are tested for their ability to retain water asdescribed in Example 1. The height of water retained by plates withcoarse visible borders are given in Table 3.

The use of coarse materials to etch and activate the surface of glassplates produces a visible border without the use of chemicals thatrequire special handling and disposal. Sandblasting with coarse materialto produce a visible edge also provides a means by which to formspill-resistant borders or barriers on glass with the ability to retaingreater than 4.5 mm of water for a number of silanizing agents. SeeTable 3.

TABLE 3 Coarse-Blasted and Nine Different Silanes Water Border MolecularHeight Etchant pH Appearance Silane Formula (mm) Coarse N/A Nice VisibleSIT 8174 C₈H₄Cl₃F₁₃Si 4.78 Grit Tridecafluoro-1,1,2,2-TetrahydrooctylSandblast Trichlorosilane N/A Nice Visible SIT 8175 C₁₄H₁₉F₁₃O₃Si 3.83Tridecafluoro-1,1,2,2-Tetrahydrooctyl Trimethoxysilane N/A Nice VisibleSIT 8176 C₁₁H₁₃F₁₃O₃Si 3.77 Tridecafluoro-1,1,2,2-TetrahydrooctylTriethoxysilane N/A Nice Visible SIO 6645 n-Octadecyl TrimethoxysilaneC₂₁H₄₆O₃Si₃ 4.09 N/A Nice Visible SIO 6715 n-Octyl TriethoxysilaneC₁₄H₃₂O₃Si₃ 3.28 N/A Nice Visible SIN 6597.4 NonafluorohexyldimethylC₁₀H₁₆F₉NSi 4.25 (dimethylamino) silane N/A Nice Visible SIH 5840.5C₁₄H₁₆F₁₇NSi 4.56 Heptadecafluorotetrahydrodecyldimethyl (dimethylamino)silane N/A Nice Visible SIH 5841.7 C₁₆H₂₂F₁₇N₃Si 4.78Heptadecafluoro-1,1,2,2,- Tetrahydrodecyltris (dimethylamino) silane N/ANice Visible SIT 8173 Tridecafluoro-1,1,2,2- C₈H₇F₁₃Si 4.66Tetrahydrooctyl silane

Example 4 A Fine Visible Spill-Resistant Border Formed at the Edge ofGlass Plates Employing Sand Blasting as a Means to Activate the GlassSurface

Eight plates are prepared for silanization as in Example 3 substitutingfine grit sand (300 mesh) in place of the coarse grit material used inthat example. The borders of the plates are each treated with one ofeight different silanes and cured at 200° F. for 15-30 min. Aftercooling, the mask is removed to reveal that fine grit sandblastingprovides a fine visible border. The height of water retained on theplates by the silanized borders is measured. The data for waterretention is shown Table 4.

As with coarse sandblasting in Example 3, the use of fine materials toetch and activate the surface of the glass plates produces a visibleborder. Sandblasting with fine mesh also provides a means by which toform spill-resistant border or barriers on glass with the ability toretain greater than about 4 mm of water for a number of silanes. Seetable 4.

TABLE 4 Fine-Blasted and Eight Different Silanes Water Border MolecularHeight Etchant pH Appearance Silane Formula (mm) Fine Grit N/A NiceVisible SIT 8174 C₈H₄Cl₃F₁₃Si 4.86 SandblastTridecafluoro-1,1,2,2-Tetrahydrooctyl Trichlorosilane N/A Nice VisibleSIT 8175 C₁₄H₁₉F₁₃O₃Si 3.92 (Tridecafluoro-1,1,2,2-TetrahydrooctylTrimethoxysilane N/A Nice Visible SIT 8176 C₁₁H₁₃F₁₃O₃Si 3.90Tridecafluoro-1,1,2,2-Tetrahydrooctyl Triethoxysilane N/A Nice VisibleSIO 6645 C₂₁H₄₆O₃Si₃ 4.01 n-Octadecyl Trimethoxysilane N/A Nice VisibleSIO 6715 C₁₄H₃₂O₃Si₃ 3.32 n-Octyl Triethoxysilane N/A Nice Visible SIH5840.5 C₁₄H₁₆F₁₇NSi 3.86 Heptadecafluorotetrahydrodecyldimethyl(dimethylamino) silane N/A Nice Visible SIH 5841.7 C₁₆H₂₂F₁₇N₃Si 4.51Heptadecafluoro-1,1,2,2,-Tetrahydrodecyltris (dimethylamino) silane N/ANice Visible SIT 8173 C₈H₇F₁₃Si 3.85Tridecafluoro-1,1,2,2-Tetrahydrooctyl silane

Example 5 Spill-Resistant Border Formation withTridecafluoro-1,1,2,2-Tetrahydrooctyl Trichlorosilane after Activationof Glass Surfaces by Chemical Etching, Abrasion, and Combined Treatments

A series of 4 inch by 4 inch glass plates are masked as described inExample 1 leaving a 0.5 inch border exposed around their outer margin,washed with water, and dried. The plates are then subject to one of thetreatments described below to activate the border region. Afteractivation the plates are treated withtridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane (product referenceSIT 8174 from Gelest), cured at 200° F. for 15 to 30 minutes. Aftercooling the mask are removed, and the height of water retained by theborder applied to those plates is measured. See Table 5 which correlatesthe height of water retained with the appearance of the border resultingfrom the treatment listed below:

-   -   1. 5% HF etching for 30 seconds produces a clear or invisible        border;    -   2. Treatment with “New Improved Armour Etch” (Armour Products,        Hawthorn, N.J.), which is an inorganic fluoride, titanium        dioxide, and citric acid composition, for 2-5 minutes produces a        visible border;    -   3. Treatment with GALLERY GLASS® etching medium (Plaid        Enterprises, Inc., Norcross, Ga.) for 1-3 minutes produces a        clear border that is not visible, very similar to that produced        by 5% HF;    -   4. Treatment with Professional 30 second Glass Etching Cream        (Martronic Corp, Salkum, Wash.) for 30 seconds produces a        visible border;    -   5. Treatment with ETCHALL® Etching Cream (B & B Products, Inc.,        Peoria, Ariz.) for up to 15 minute produces a visible border;    -   6. 1 N NaOH etching for 5-7 minutes produces a clear or        invisible border;    -   7. 5% aqueous sodium silicate, for 2-5 minutes also known as        water glass, etches glass and produces a clear invisible border;    -   8. The hydroxyl radical generating system, VTX catalyst        (Advanced Oxidation Technology, Inc., Fredericksburg, Va.)        (amount used) and H₂O₂ (3%??? w/w) when used in combination to        activate glass prior to silanization produces a clear or        invisible border;    -   9. Treatment by coarse grit sandblasting (43 mesh sand) produced        a highly visible border with a rough appearance;    -   10. Treatment by coarse grit sandblast followed by sodium        silicate etching is conducted by coarse grit sandblasting (43        mesh sand) as in treatment 9, supra, to produce a highly visible        border with a rough appearance. The border produced by the        sandblasting is subsequently etched using 5% aqueous sodium        silicate for 2 minutes and 30 seconds;    -   11. Treatment by fine grit sandblasting (300 grit SiC particles)        produced a visible border;    -   12. Treatment by etching with 5% HF in the presence of 20% w/v        of thermoplastic powder (512 powder, 10-100 micron size, XIOM        Corp. and NY) for 1-2 minutes produced a clear border;    -   13. Treatment by fine grit sandblast followed by sodium silicate        etching is conducted by fine grit sandblasting as in treatment        11, supra, to produce a visible border. The border produced by        the sandblasting is subsequently etched using 5% aqueous sodium        silicate for 2 minutes and 30 seconds;    -   14. Treatment by fine grit sandblast followed by aqueous sodium        hydroxide (NaOH 5% w/v) etching is conducted by fine grit        sandblasting as in treatment 11, supra, to produce a visible        border. The border produced by the sandblasting is subsequently        etched using 5% aqueous sodium hydroxide for 2 minutes and 30        seconds.        The height of water retained by the various glass plates are        plotted as a function of pH of the etchant used in FIG. 4. That        plot indicates that the water height data are basically        independent of the etchant's pH.

TABLE 5 Silane SIT8174 Water Broader Border Molecular Height Etchants pHAppearance Silane Formula (mm) 5% HF Etch 1 Clear SIT 8174 C₈H₄Cl₃F₁₃Si4.69 Tridecafluoro-1,1,2,2-Tetrahydrooctyl Trichlorosilane New 3 NiceVisible SIT 8174 C₈H₄Cl₃F₁₃Si 4.80 ImprovedTridecafluoro-1,1,2,2-Tetrahydrooctyl Armour Etch TrichlorosilaneGallery Glass 9 Clear SIT 8174 C₈H₄Cl₃F₁₃Si 4.78 window etchTridecafluoro-1,1,2,2-Tetrahydrooctyl Trichlorosilane Professional 3Nice Visible SIT 8174 C₈H₄Cl₃F₁₃Si 4.70 30s glassTridecafluoro-1,1,2,2-Tetrahydrooctyl etching Trichlorosilane Etchall 3Nice Visible SIT 8174 C₈H₄Cl₃F₁₃Si 3.98 etchingTridecafluoro-1,1,2,2-Tetrahydrooctyl cream Trichlorosilane 1N NaOH 14Clear SIT 8174 C₈H₄Cl₃F₁₃Si 3.89 Tridecafluoro-1,1,2,2-TetrahydrooctylTrichlorosilane Sodium 12.5 Clear SIT 8174 C₈H₄Cl₃F₁₃Si 4.50 SilicateTridecafluoro-1,1,2,2-Tetrahydrooctyl Trichlorosilane VTX 7 Clear SIT8174 C₈H₄Cl₃F₁₃Si 4.15 Tridecafluoro-1,1,2,2-TetrahydrooctylTrichlorosilane Coarse Grit N/A Nice Visible SIT 8174 C₈H₄Cl₃F₁₃Si 4.78Sandblast Tridecafluoro-1,1,2,2-Tetrahydrooctyl Trichlorosilane CoarseGrit N/A Nice Visible SIT 8174 C₈H₄Cl₃F₁₃Si 4.27 SandblastTridecafluoro-1,1,2,2-Tetrahydrooctyl with Sodium TrichlorosilaneSilicate Fine Grit N/A Nice Visible SIT 8174 C₈H₄Cl₃F₁₃Si 4.86 SandblastTridecafluoro-1,1,2,2-Tetrahydrooctyl Trichlorosilane 5% HF (with 1Clear SIT 8174 C₈H₄Cl₃F₁₃Si 4.47 512 PowerTridecafluoro-1,1,2,2-Tetrahydrooctyl coat Trichlorosilane Fine Grit12.5 Nice Visible SIT 8174 C₈H₄Cl₃F₁₃Si 4.57 SandblastTridecafluoro-1,1,2,2-Tetrahydrooctyl with Sodium TrichlorosilaneSilicate Fine Grit 14 Nice Visible SIT 8174 C₈H₄Cl₃F₁₃Si 4.02 SandblastTridecafluoro-1,1,2,2-Tetrahydrooctyl with NaOH Trichlorosilane

Example 6 Spill-Resistant Border Formation withTridecafluoro-1,1,2,2-Tetrahydrooctyl Trimethoxysilane after Activationof Glass Surfaces by Chemical Etching, Abrasion, and Combined Treatments

The ability of plates having borders prepared withtridecafluoro-1,1,2,2-tetrahydrooctyl trimethoxysilane (Gelest productreference SIT8176) under the conditions described in Table 6 to retainwater is conducted using six glass plates. The plates are masked leavinga 0.5 inch border at their edge and treated using SIT8176 as thesilanizing agent using the methods employed in Example 5. The height ofwater retained on these plates and the pH of the etchant, whereapplicable, is listed in Table 6.

TABLE 6 Silane SIT8176 Water Broader Border Molecular Height Etchants pHAppearance Silane Formula (mm) VTX 7 Clear SIT8176 C₁₄H₁₉F₁₃O₃Si 3.16Tridecafluoro-1,1,2,2-Tetrahydrooctyl Trimethoxysilane Coarse Grit N/ANice Visible SIT8176 C₁₄H₁₉F₁₃O₃Si 3.83 SandblastTridecafluoro-1,1,2,2-Tetrahydrooctyl Trimethoxysilane Coarse Grit N/ANice Visible SIT8176 C₁₄H₁₉F₁₃O₃Si 3.32 SandblastTridecafluoro-1,1,2,2-Tetrahydrooctyl with Sodium TrimethoxysilaneSilicate Fine Grit N/ Nice Visible SIT8176 C₁₄H₁₉F₁₃O₃Si 3.92 SandblastTridecafluoro-1,1,2,2-Tetrahydrooctyl Trimethoxysilane Fine Grit 12.5Nice Visible SIT8176 C₁₄H₁₉F₁₃O₃Si 3.92 SandblastTridecafluoro-1,1,2,2-Tetrahydrooctyl with Sodium TrimethoxysilaneSilicate Fine Grit 14 Nice Visible SIT8176 C₁₄H₁₉F₁₃O₃Si 2.97 SandblastTridecafluoro-1,1,2,2-Tetrahydrooctyl with NaOH Trimethoxysilane

Example 7 Spill-Resistant Border Formation withTridecafluoro-1,1,2,2-Tetrahydrooctyl Triethoxysilane after Activationof Glass Surfaces by Chemical Etching, Abrasion, and Combined Treatments

Spill-resistant borders are prepared on glass plates as in example 6using tridecafluoro-1,1,2,2-tetrahydrooctyl triethoxysilane (Gelestreference SIT8175) in place of tridecafluoro-1,1,2,2-tetrahydrooctyltrimethoxysilane. Data for this example are summarized in Table 7.tridecafluoro-1,1,2,2-tetrahydrooctyl triethoxysilane produce lowerwater heights than tridecafluoro-1,1,2,2-tetrahydrooctyltrimethoxysilane (SIT8176). Post-blast etching reductions in waterheight are similar to those in Examples 5 and 6.

TABLE 7 Silane SIT8175 Water Broader Border Molecular Height Etchants pHAppearance Silane Formula (mm) VTX 7 Clear SIT 8175 C₁₁H₁₃F₁₃O₃Si 2.85Tridecafluoro-1,1,2,2- Tetrahydrooctyl Triethoxysilane Coarse Grit N/ANice Visible SIT 8175 C₁₁H₁₃F₁₃O₃Si 3.77 SandblastTridecafluoro-1,1,2,2- Tetrahydrooctyl Triethoxysilane Coarse Grit N/ANice Visible SIT 8175 C₁₁H₁₃F₁₃O₃Si 3.12 Sandblast withTridecafluoro-1,1,2,2- Sodium Silicate Tetrahydrooctyl TriethoxysilaneFine Grit N/A Nice Visible SIT 8175 C₁₁H₁₃F₁₃O₃Si 3.90 SandblastTridecafluoro-1,1,2,2- Tetrahydrooctyl Triethoxysilane Fine Grit 12.5Nice Visible SIT 8175 C₁₁H₁₃F₁₃O₃Si 3.78 Sandblast withTridecafluoro-1,1,2,2- Sodium Silicate Tetrahydrooctyl TriethoxysilaneFine Grit 14 Nice Visible SIT 8175 C₁₁H₁₃F₁₃O₃Si 3.12 Sandblast withTridecafluoro-1,1,2,2- NaOH Tetrahydrooctyl Triethoxysilane

Example 8 Spill-Resistant Border Formation with n-OctadecylTrimethoxysilane after Activation of Glass Surfaces by Chemical Etching,Abrasion, and Combined Treatments

The ability of plates having borders prepared with n-octadecyltrimethoxysilane (Gelest product reference SIO 6645) to retain waterunder the conditions described in Table 8 is conducted using six glassplates. The plates are masked leaving a 0.5 inch border at their edgeand treated using SIO 6645 as the silanizing agent using the indicatedmethods in Example 5. The height of water retained on these plates andthe pH of the etchant, where applicable, is listed in Table 8.

TABLE 8 Silane SIO6645 Water Broader Border Molecular Height Etchants pHAppearance Silane Formula (mm) New 3 Nice Visible SIO 6645 C₂₁H₄₆O₃Si₃3.91 Improved n-Octadecyl Trimethoxysilane Armour Etch Gallery glass 9Clear SIO 6645 C₂₁H₄₆O₃Si₃ 3.97 window n-Octadecyl Trimethoxysilane etchProfessional 3 Nice Visible SIO 6645 C₂₁H₄₆O₃Si₃ 4.07 30s glassn-Octadecyl Trimethoxysilane etching Etchall 3 Nice Visible SIO 6645C₂₁H₄₆O₃Si₃ 3.94 etching n-Octadecyl Trimethoxysilane cream 10N NaOH 14Clear SIO 6645 C₂₁H₄₆O₃Si₃ 3.96 n-Octadecyl Trimethoxysilane Sodium 12.5Clear SIO 6645 C₂₁H₄₆O₃Si₃ 3.96 Silicate n-Octadecyl TrimethoxysilaneVTX 7 Clear SIO 6645 C₂₁H₄₆O₃Si₃ 3.91 n-Octadecyl TrimethoxysilaneCoarse Grit N/A Nice Visible SIO 6645 C₂₁H₄₆O₃Si₃ 4.09 Sandblastn-Octadecyl Trimethoxysilane Coarse Grit N/A Nice Visible SIO 6645C₂₁H₄₆O₃Si₃ 3.86 Sandblast n-Octadecyl Trimethoxysilane with SodiumSilicate Fine Grit N/A Nice Visible SIO 6645 C₂₁H₄₆O₃Si₃ 4.01 Sandblastn-Octadecyl Trimethoxysilane Fine Grit 12.5 Nice Visible SIO 6645C₂₁H₄₆O₃Si₃ 4.03 Sandblast n-Octadecyl Trimethoxysilane with SodiumSilicate Fine Grit 14 Nice Visible SIO 6645 C₂₁H₄₆O₃Si₃ 3.16 Sandblastn-Octadecyl Trimethoxysilane with NaOH

Example 9 Spill-Resistant Border Formation with n-OctadecylTriethoxysilane after Activation of Glass Surfaces by Chemical Etching,Abrasion, and Combined Treatments

The ability of plates having borders prepared with n-octyltriethoxysilane (Gelest product reference SIO 6715) to retain water isassessed using twelve glass plates treated with one of the conditionsset forth in Table 9. The plates are masked leaving a 0.5 inch border attheir edge and treated using SIO 6715 as the silanizing agent using themethods employed in Example 5. The height of water retained on theseplates and the pH of the etchant, where applicable, is listed in Table9.

TABLE 9 Silane SIO6715 Water Broader Border Molecular Height Etchants pHAppearance Silane Formula (mm) New 3 Nice Visible SIO 6715 n-OctylTriethoxysilane C₁₄H₃₂O₃Si₃ 3.85 Improved Armour Etch Gallery Glass 9Clear SIO 6715 n-Octyl Triethoxysilane C₁₄H₃₂O₃Si₃ 4.06 window etchProfessional 3 Nice Visible SIO 6715 n-Octyl Triethoxysilane C₁₄H₃₂O₃Si₃3.96 30s glass etching Etchall 3 Nice Visible SIO 6715 n-OctylTriethoxysilane C₁₄H₃₂O₃Si₃ 3.86 etching cream 10N NaOH 14 Clear SIO6715 n-Octyl Triethoxysilane C₁₄H₃₂O₃Si₃ 3.25 Sodium 12.5 Clear SIO 6715n-Octyl Triethoxysilane C₁₄H₃₂O₃Si₃ 3.48 Silicate VTX 7 Clear SIO 6715n-Octyl Triethoxysilane C₁₄H₃₂O₃Si₃ 3.59 Coarse Grit N/A Nice VisibleSIO 6715 n-Octyl Triethoxysilane C₁₄H₃₂O₃Si₃ 3.28 Sandblast Coarse GritN/A Nice Visible SIO 6715 n-Octyl Triethoxysilane C₁₄H₃₂O₃Si₃ 3.12Sandblast with Sodium Silicate Fine Grit N/A Nice Visible SIO 6715n-Octyl Triethoxysilane C₁₄H₃₂O₃Si₃ 3.32 Sandblast Fine Grit 12.5 NiceVisible SIO 6715 n-Octyl Triethoxysilane C₁₄H₃₂O₃Si₃ 4.14 Sandblast withSodium Silicate Fine Grit 14 Nice Visible SIO 6715 n-OctylTriethoxysilane C₁₄H₃₂O₃Si₃ 3.12 Sandblast with NaOH

Example 10 Abrasion with Fine Polishing Powders as a Means of ActivatingGlass Surfaces for the Formation of Spill-Resistant Borders

Four 4 inch by 4-inch square glass plates are masked with electricaltape to create a 0.5-inch wide spill-resistant border at the outer edge.The area that will form the border is polished using slurry of about60-70 gram of cerium oxide in water (3.5-3.7 micron particles, about3,000-8,000 mesh or grit). Polishing is carried out by using a motorizedwheel with the surface of the plate being polished soaked with theslurry.

Following abrasion/polishing with cerium oxide, two of the four platesare etched with 5% aqueous HF solution for 30 seconds. The polished andpolished/etched plates are washed with water and dried first with astream of air and then in a 200° F. oven for 5 min. One each of thepolished and polished/etched plates is treated with the silanizing agentSIT8174 or silanizing agent SIH5841.7. The treated plates are cured byheating at 200° F. for 15-30 min. Data for all four plates aresummarized in Table 10. The agent SIT8174 performed slightly better thanSIH5841.7 for both sets of plates.

TABLE 10 Spill-Resistant Borders Prepared by Cerium Oxide Polishing Withand Without 5% HF Etch Employing Two Different Silane Treatments BorderWater Border Treatment pH Silane Formula Height (mm) Appearance Ceriumoxide polish N/A SIT8174 C₈H₄Cl₃F₁₃Si 4.46 Clear Cerium oxide & 5% HF 1SIT8174 C₈H₄Cl₃F₁₃Si 4.53 Clear etch Cerium oxide N/A SIH5841.7C₁₆H₂₂F₁₇N₃Si 4.31 Clear Cerium oxide & 5% HF 1 SIH5841.7 C₁₆H₂₂F₁₇N₃Si4.38 Clear etch

Example 11 The Ability of Spill-Resistant Borders to Retain AlcoholContaining Liquids

Four 4 inch x 4-inch glass plates with spill-resistant borders areprepared by four different methods indicated in Table 11 as described inExample 5 and silanated with tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (SIT8174). The plates are tested for their spillperformance with two alcoholic beverages; a wine (Sutter Home Merlot,Calif., 2007) and vodka (Krasser's Vodka). Spill height data for thosealcoholic drinks are summarized in Table 11. Wine with its lower alcoholcontent shows a higher retained liquid level than the vodka with itshigher alcohol content. The coarse grit sandblasted borders show thehighest retained liquid heights for both liquids.

TABLE 11 Spill Barrier Height for Two Alcoholic Beverages Water BorderBorder Height Appear- Treatment pH Silane Formula (mm) ance Sutter HomeMerlot (California, 2007) 5% HF 1 SIT8174 C₈H₄Cl₃F₁₃Si 3.54 Clear Sodiumsilicate 12.5 SIT8174 C₈H₄Cl₃F₁₃Si 3.69 Clear Coarse grit blast N/ASIT8174 C₈H₄Cl₃F₁₃Si 4.02 Visible Fine grit blast N/A SIT8174C₈H₄Cl₃F₁₃Si 3.58 Visible Krasser's Vodka 5% HF 1 SIT8174 C₈H₄Cl₃F₁₃Si2.53 Clear Sodium silicate 12.5 SIT8174 C₈H₄Cl₃F₁₃Si 2.53 Clear Coarsegrit blast N/A SIT8174 C₈H₄Cl₃F₁₃Si 2.66 Visible Fine grit blast N/ASIT8174 C₈H₄Cl₃F₁₃Si 2.63 Visible

Example 12 The Ability of Spill-Resistant Borders to Retain VariousLiquid Food Items after Cleaning

Four groups three of 4 inch by 4 inch square plates, having a 0.5 inchspill-resistant border formed by the application oftridecafluoro-1,1,2,2-tetrahydrooctyl tricholorosilane to their edgesafter one of the following four treatments. In the first treatment,three plates are masked leaving a 0.5 inch region at the edge exposedfor the preparation of the spill-resistant border. The plate is etchedwith 5% aqueous HF for 30 seconds at room temperature. The second set ofthree plates is masked as described for the first treatment in thisexample and subject to sandblasting with 400 mesh abrasive particles andsubsequently etched with 5% aqueous HF for 30 seconds at roomtemperature. The third set of three plates is masked as described forthe first treatment in this example and subject to sandblasting with 35mesh abrasive particles and subsequently etched with 5% aqueous HF for30 seconds at room temperature. The fourth set of plates are masked asdescribed for the first treatment in this example and subject tosandblasting with 35 mesh abrasive particles without subsequent etching.

After the above treatments, and before removing the masks, the platesare washed with water, and dried in an oven (about 200° F.) for about 15minutes. After cooling, the plates are treatedtridecafluoro-1,1,2,2-tetrahydrooctyl tricholorosilane as a 1% solutionin hexane. After the hexane has evaporated the plates are cured bybaking in an oven at 150 to 250° F. for 5 to 30 minutes (curing can alsobe accomplished by allowing the silanated plates to remain at roomtemperature for about 24 hours in a controlled humidity environment).Following curing masks are removed. The ability of each set of threeplates to retain water is measured and the average values for the heightof water retained is plotted for each plate in the histogram shown inFIG. 5 and the average for each treatment is shown FIG. 6.

Using the following sequence of cleaning and filling with various foodstuffs, the ability of the plates to retain liquids (resistance tospillage) is assessed for each type of plate and food stuff:

-   -   i) Cleaning with soap and water,    -   ii) Filling with water (see data for the height of retained        water in Table 12a),    -   iii) Cleaning with soap and water,    -   iv) Filling with apple juice (see data for the height of        retained apple juice in Table 12b),    -   v) Cleaning with soap and water,    -   vi) Filling with oil and vinegar salad dressing with spices (see        data for the height of retained salad dressing in Table 12c),    -   vii) Cleaning with soap and water,    -   viii) Filling with milk (see data for the height of retained        milk in Table 12d), vii) Cleaning with soap and water,    -   ix) Cooling the plates and water to approximately 36° F.        overnight and filling the plates with the cooled water without        removing any condensation from their surfaces (see data for the        height of retained cooled water in Table 12e), and    -   x) Drying the condensation present on the plates and filling        them with ice cold water (see data for the height of retained        ice cold water in Table 12f).

TABLE 12a Retention of water after one cleaning with soap and waterVolume of Water Water Height Filled in Spill Area In Spill Water SpillArea Prior to Volume/Spill Spill Area (mm) Area Spill Area TreatmentWidth Length (cm²) (cm³) (mm) 1 28.30 41.19 11.66 4.8 4.12 2 22.73 46.7810.63 4.8 4.51 3 18.64 45.13 8.41 5.0 5.94 4 18.93 47.08 8.91 4.0 4.49

TABLE 12b Retention of apple juice after cleaning with soap Volume ofWater Water Height Filled in Spill Area In Spill Water Spill Area Priorto Volume/Spill Spill Area (mm) Area Spill Area Treatment Width Length(cm²) (cm³) (mm) 1 28.30 41.19 11.66 4.8 4.12 2 22.73 46.78 10.63 4.84.51 3 18.64 45.13 8.41 5.0 5.94 4 18.93 47.08 8.91 4.0 4.49

TABLE 12c Retention of salad dressing after cleaning with soap and waterVolume of Water Water Height Filled in Spill Area In Spill Water SpillArea Prior to Volume/Spill Spill Area (mm) Area Spill Area TreatmentWidth Length (cm²) (cm³) (mm) 1 29.59 54.52 16.13 5.8 3.60 2 28.30 41.1911.66 4.7 4.03 3 22.73 46.78 10.63 4.8 4.51 4 18.64 45.13 8.41 4.4 5.235 18.93 47.08 8.91 3.0 3.37

TABLE 12d Retention of milk after cleaning with soap and water Volume ofWater Water Height Filled in Spill Area In Spill Water Spill Area Priorto Volume/Spill Spill Area (mm) Area Spill Area Treatment Width Length(cm²) (cm³) (mm) 1 28.30 41.19 11.66 3.6 3.09 2 22.73 46.78 10.63 3.93.67 3 18.64 45.13 8.41 4.0 4.76 4 18.93 47.08 8.91 3.0 3.37

TABLE 12e Retention of cooled water after cleaning with soap and water(without removing condensation) Volume of Water Water Height Filled inSpill Area In Spill Water Spill Area Prior to Volume/Spill Sample SpillArea (mm) Area Spill Area ID Width Length (cm²) (cm³) (mm) 1 28.30 41.1911.66 1.6 1.37 2 22.73 46.78 10.63 3.4 3.20 3 18.64 45.13 8.41 3.9 4.644 18.93 47.08 8.91 2.9 3.25

TABLE 12f Retention of ice cold water after removing condensation Volumeof Water Water Height Filled in Spill Area In Spill Water Spill AreaPrior to Volume/Spill Sample Spill Area (mm) Area Spill Area ID WidthLength (cm²) (cm³) (mm) 1 28.30 41.19 11.66 4.7 3.99 2 22.73 46.78 10.634.6 4.32 3 18.64 45.13 8.41 4.2 4.99 4 18.93 47.08 8.91 3.8 4.26

Example 13 The Effects of Abrasion on the Ability of Spill-ResistantBorders to Retain Water

Part A—A second of the glass plates are prepared using each of the fourtreatments described in Example 12, is assessed for their ability toretain water (see the middle bar for each treatment group in FIG. 5. Theplates are subject to abrasion using a glass jar by moving it back andforth over the border 5 times and the height of water retained by theborder on those plates is measured again. From the data in Table 13 andFIG. 7 it can be seen that rubbing can reduce the water height to someextent.

TABLE 13A Testing water retention of a spill-resistant border afterabrasion with a glass jar five times Volume of Water Water Height Filledin Spill Area In Spill Water Spill Area Prior to Volume/Spill Spill Area(mm) Area Spill Area Treatment Width Length (cm²) (cm³) (mm) 1 15.4538.78 5.99 2.3 3.84 2 18.95 43.15 8.18 3.8 4.65 3 17.30 43.17 7.47 3.44.55 4 18.39 45.53 8.37 4.1 4.90

Part B—A 0.5 inch spill-resistant borders is prepared on the edge three4-by 4-in, glass plates using as activation treatments (i) 0 5% HFetching produced a clear border, (ii) sandblasting using find sandproduced a visible border by abrasion, and (iii) Professional 30 SecondGlass Etch to form a visible border. The activated borders regions ofeach plate are treated with silane SIT8174 from Gelest, Inc.

For each plate, border abrasion tests are carried with using a 32-oz.glass jar filled (a “Mason Jar”) filled with 24 oz. of water. After aninitial measurement of water fill height for each plate, the jar isrubbed over the border on one side of the plate 50, 100, 150, 200 and300 times for with the height of water retained by the plate measuredafter each set of rubbing. Data are shown in Table 13B.

TABLE 13B Height of water retained in millimeter for the numbers of rubsindicated in parentheses Glass Plate (control Sample No. Border Type 0rubs) (50) (100) (150) (200) (300) 1 Invisible 4.7 4.65 4.33 4.33 4.334.17 3 Visible 4.86 4.81 4.81 4.81 4.81 4.81 (Sand) 5 Visible 4.7 4.814.65 4.49 4.49 4.49 Professional 30 sec. Glass Etch

Example 14 The Hydrophobic and Oleophobic Behavior Treated Surfaces

Water and mineral oil contact angle data are measured for on 2 inch by 2inch glass plates that have been treated with one of nine differentsilanizing agents. Prior to treatment with silanizing agents the platesare activated by etching the surface with 5% aqueous HF for 30 seconds,drying at 200° F. for 15-30 minutes, cooling, and treating the plateswith one of nine the different silanes in Table 14(a). After treatmentwith silanes, the plates are cured at 200° F. for 15 to 30 minutes andcooled. Ten measurements of the contact angles for water and mineral oil(Mineral Oil, Light Viscosity, Technical Grade, PTI Process Chemicals,Ringwood, Ill.) are made on each plate. The averages and standarddeviations for those measurements are summarized in Table 14(a), whichalso includes data for glass that has not been treated with a silanizingagent as the “Control No Silanization” entry. All measurements are madeat room temperature.

TABLE 14(a) Contact Angle for glass surfaces treated with one of ninedifferent silanes to form a border region that is not visible TerminalStd. Silane ID: Leaving Group Functionality Average Deviation WaterContact Angle (degrees) SIT8173.0 Trihydro Fluorine (13) 91.569 6.1189SIT8174.0 Trichloro Fluorine (13) 116.212 3.2937 SIT8175.0 TriethoxyFluorine (13) 64.5037 8.0617 SIT8176.0 Trimethoxy Fluorine (13) 91.7226.8284 SIH5840.5 Dimethylamino Fluorine (17) 81.006 8.5750 SIH5841.7Tris(dimethylamino) Fluorine (17) 85.491 8.6567 SIO6645.0 TrimethoxyMethyl (18) 83.045 10.6766 SIO6715.0 Triethoxy Methyl (18) 62.49120.9539 SIN6597.4 Dimethylamino Fluorine (9) 59.7741 5.6127 Control No —— 18.395 1.4045 Silanization Oil Contact Angle (degrees) SIT8173.0Trihydro Fluorine (13) 72.0708 7.0987 SIT8174.0 Trichloro Fluorine (13)108.7258 3.0468 SIT8175.0 Triethoxy Fluorine (13) 33.1158 3.1323SIT8176.0 Trimethoxy Fluorine (13) 55.3158 7.2287 SIH5840.5Dimethylamino Fluorine (17) 41.068 2.8977 SIH5841.7 Tris(dimethylamino)Fluorine (17) 56.337 3.7703 SIO6645.0 Trimethoxy Methyl (18) 34.5311.0548 SIO6715.0 Triethoxy Methyl (18) 34.6855 1.0308 SIN6597.4Dimethylamino Fluorine (9) 27.0033 7.2239 Control No — — 12.341 3.6562Silanization *Control measurement was made on the surface not subjectedto HF treatment

Water and mineral oil contact angle data are measured on 2 inch by 2inch glass plates prepared using one of the following three activatingtreatments:

-   -   1. Blasting with fine sand (57.5 μm);    -   2. Blasting with coarse sand (387.5 μm); and    -   3. Etching using 30 Sec Etching Cream        Following the activation treatment, the plates are treated with        one of three different fluorinated alkyl silanizing agents (SIH        5840.5, SIH 5841.7, and SIT 8174.0) to convert the surface into        hydrophobic or oleophobic surfaces such as would be used in a        spill-resistant border. For plates blasted with coarse sand, a        non-fluorinated silane (SIO 6715.0) is also employed to convert        the surface into a spill resistant border. After treatment with        the silanizing agents, the plates are cured at 200° F. for 15 to        30 minutes and cooled. Five measurements of the contact angles        for water and mineral oil are made on each plate. The averages        and standard deviations for those measurements are summarized in        Table 14(b), which also includes data for glass that has not        been treated with a silanizing agent. All measurements are made        at room temperature.

TABLE 14(b) Contact Angle for glass surfaces treated with silanes toform a visible border region Contact Angle (degrees) Silane ID: VisibleBorder Liquid Average Std. Deviation SIH 5840.5 Fine Blast water 76.935.797098 SIH 5840.5 Corse Blast water 71.37 3.014489 SIH 5840.5 30 Sec.Etching Cream water 46.41 4.425683 SIH 5841.7 Fine Blast water 112.641.951766 SIH 5841.7 Corse Blast water 106.79 2.053628 SIH 5841.7 30 Sec.Etching Cream water 108.01 11.83157 SIT 8174.0 Fine Blast water 123.742.899724 SIT 8174.0 Corse Blast water 124.72 3.995871 SIT 8174.0 30 Sec.Etching Cream water 110.87 1.73312 SIO 6715.0 Corse Blast 85.22 1.815218Control No Silanization Fine Blast water 26.25 11.89606 Control NoSilanization Corse Blast water 41.61 6.504281 Control No Silanization 30Sec. Etching Cream water 33.35 1.308337 SIH 5840.5 Fine Blast mineraloil 29.71 4.563883 SIH 5840.5 Corse Blast mineral oil 26.25 2.987117 SIH5840.5 30 Sec. Etching Cream mineral oil 38.13 5.513698 SIH 5841.7 FineBlast mineral oil 52.73 4.227723 SIH 5841.7 Corse Blast mineral oil79.85 3.850016 SIH 5841.7 30 Sec. Etching Cream mineral oil 75.819.344477 SIT 8174.0 Fine Blast mineral oil 88.22 4.614441 SIT 8174.0Corse Blast mineral oil 91.88 1.734779 SIT 8174.0 30 Sec. Etching Creammineral oil 85.75 4.597758 SIO 6715.0 Corse Blast mineral oil 10.510.398026 Control No Silanization Fine Blast mineral oil Less than 10 —Control No Silanization Corse Blast mineral oil 13.66 1.212068 ControlNo Silanization 30 Sec. Etching Cream mineral oil 16.21 2.340523*Control measurements are made on the surface after blasting or etching

Example 15 Spill-Resistant Borders and their Behavior with Oils

The behavior of spill-resistant borders with oils is assessed bydetermining the height of a mineral oil layer that the border will causeto be retained without spillage. For the assessment, 0.5 inch bordersare formed on the edge of masked 4 inch by 4 inch glass plates. Theregion that will form the border on three of the plates is activatedwith 5% aqueous HF, two of which are treated with a fluorine containingsilanizing agents and one with a non-fluorine containing silanizingagent. The region that will form the border on the remaining threeplates is activated by sandblasting with 60 mesh particles, followed bytreatment with the same three silanes employed for the HF activatedplates. The mineral oil height and contact angle data obtained for allsix samples is summarized in Table 15.

TABLE 15 Mineral Oil Height for Borders on Glass with Two DifferentActivators and Three Different Silanes Height Contact Standard Plate IDSilane Formula (mm) Angle (Θ) Deviation Sand Blast 8174 C₈H₄C₁₃F₁₃Si2.38 Sand Blast 5841.7 C₁₆H₂₂F₁₇N₃Si 2.06 Sand Blast 6715.0 C₁₄H₃₂O₃Si₃0.95 (Non-F) HF 8174 C₈H₄C₁₃F₁₃Si 1.91 108.7 3.04 HF 5841.7C₁₆H₂₂F₁₇N₃Si 2.05 56.34 3.77 HF 6715.0 (Non-F) C₁₄H₃₂O₃Si₃ 1.17 34.71.03 *Non-F indicates the terminal functionality contained no fluorineatoms.

Example 16 The Effect of Leaving Silanizing Agent Groups on the WaterRetention of Spill-Resistant Borders Formed on Glass Surfaces

The effectiveness of silane leaving groups and terminal functionalitieson the ability of spill-resistant borders to retain water is assessedfor nine different silanes under controlled conditions. For theassessment, nine 4 inch by 4 inch square glass plates are masked withelectrical tape to create a 0.5-inch wide unmasked area around the outeredge as in Example 1. The unmasked area is etched with 5% HF for 1minute, the acid is washed off with cold water, and the plates are driedat about 200° F. for 15-30 minutes, followed by cooling, and treatingseparate plates with one of nine different silanes as a 1% solution ofthe silane in hexane. All of the plates are heat cured at about 200° F.for 15-30 minutes, and after cooling are unmasked and the height ofwater retained by the spill-resistant border measured. All plates areprocessed at the same time in order to minimize any treatmentdifferences that might arise. Water-height data are summarized in Table16.

TABLE 16 Water Height for Spill-Resistant Borders Created by Etchingwith 5% HF and using Nine Different Silanes Water Height LeavingTerminal No. Silane Name^(a) (mm) Group Functionality^(b) 1 SIT8173 3.92Trihydro Fluorine (13) 2 SIT8174 4.59 Trichloro Fluorine (13) 3 SIT81753.90 Triethoxy Fluorine (13) 4 SIT8176 4.00 Trimethoxy Fluorine (13) 5SIH5840.5 4.30 Dimethylamino Fluorine (17) 6 SIH5841.7 4.59Tris(dimethylamino) Fluorine (17) 7 SIO6645.0 4.08 Trimethoxy Methyl(18) 8 SIO6715.0 3.69 Triethoxy Methyl (8) 9 SIN6597.4 3.50Dimethylamino Fluorine (9) ^(a)All silanes are from Gelest and the entryunder “Silane Name” represents their Gelest references. ^(b)Numbers inparenthesis represent the number of fluorine's in the terminalfunctional groups.

Example 17 Sandblast Particle Size Versus Feature Size of Glass Borders

Three different sand particle sizes are used to create different sizefeatures in glass borders. Sands are: fine, with particle size rangingfrom 45-70 μm; coarse, with particle sizes of 250-525 μm; or medium,which is composed of a 50:50 mixture of fine and coarse sands, andyielding a particle size ranging from 45-525 μm.

Feature sizes are measured by taking 200× magnification micrographs foreach of the sandblasted borders made on 4-by 4-in, glass plates. Thesand used and feature sizes observed are summarized in Table 17.

TABLE 17 Particle Sizes and Observed Feature Sizes Sand Size AverageFeature Size in Glass Sand Type in microns (μm) Border (μm) Fine 57.560.4 Medium 222.5 109.6 Coarse 387.5 202.0

1. A method for forming a spill-resistant border on a refrigerationshelf surface comprising activating a portion of the surface by etchingor abrading it to form a roughened area on the surface and applying acomposition to at least a portion of the roughened area on the surfacethat increases the hydrophobicity and oleophobicity of at least aportion of the roughened area on the surface that forms thespill-resistant border, wherein said spill-resistant border forms aperimeter around at least one area that has a lower hydrophobicity andlower oleophobicity than the spill-resistant border; and wherein thecomposition comprises a silanizing agent that covalently binds theroughened area.
 2. The method of claim 1, further comprising applying amask to said surface either before said activating, or said applying acomposition, or before both activating a portion of the surface andapplying the composition.
 3. The method of claim 1, wherein saidactivating comprises etching the surface with a chemical agent.
 4. Themethod of claim 3, wherein said chemical agent is hydrofluoric acid.5-6. (canceled)
 7. The method of claim 2, wherein said activatingcomprises abrading the surface. 8-12. (canceled)
 13. The refrigeratorshelf surface of claim 47, wherein said spill-resistant border providesa retention of up to 5.9 mm of water.
 14. The refrigerator shelf surfaceof claim 47, wherein said spill-resistant border provides a retention ofup to 5.2 mm of a mixture comprising oil and water.
 15. The refrigeratorshelf surface of claim 47, wherein said spill resistant border providesa retention of greater than 2.9 mm of water and less than 5.94 mm ofwater after four washings with soap and water. 16-26. (canceled)
 27. Themethod of claim 1, wherein said composition comprises a silanizing agenthaving a terminal functionality that is selected from the groupconsisting of a fluoroalkyl or perfluoroalkyl.
 28. The method of claim27, wherein said silanizing agent has at least one leaving groupselected from the group consisting of chloro, —O-alkyl,—NH—(C₁-C₆alkyl), and —N—(C₁-C₆alkyl)₂.
 29. The refrigerator shelfsurface of claim 15, wherein said silanizing agent has at least onechloro leaving group.
 30. The refrigerator shelf surface of claim 15,wherein said silanizing agent, is a compound of formula (I):R_(4-n)Si—X_(n)  (I) where n is an integer from 1-3; and wherein each Ris independently selected from (i) alkyl or cycloalkyl group optionallysubstituted one or more fluorine atoms, (ii) C_(1 to 20) alkyloptionally substituted with one or more independently selectedsubstituents selected from fluorine atoms and C₆₋₁₄ aryl groups, whicharyl groups are optionally substituted with one or more independentlyselected halo, C_(1 to 10) alkyl, C_(1 to 10) haloalkyl, C_(1 to 10)alkoxy, or C_(1 to 10) haloalkoxy substituents, (iii) C_(6 to 20) alkylether optionally substituted with one or more substituents independentlyselected from fluorine and C₆₋₁₄ aryl groups, which aryl groups areoptionally substituted with one or more independently selected halo,C_(1 to 10) alkyl, C_(1 to 10) haloalkyl, C_(1 to 10) alkoxy, orC_(1 to 10) haloalkoxy substituents, (iv) C₆₋₁₄ aryl, optionallysubstituted with one or more substituents independently selected fromhalo or alkoxy, and haloalkoxy substituents; (v) C_(6 to 20) alkenyl orC_(6 to 20) alkynyl, optionally substituted with one or moresubstituents independently selected from halo, alkoxy, or haloalkoxy[N];and (vi) —Z—((CF₂)_(q)(CF₃))_(r), wherein Z is a C₁₋₁₂ divalent alkaneradical or a C₂₋₁₂ divalent alkene or alkyne radical, and q is aninteger from 1 to 12, and r is an integer from 1-4; each X isindependently selected from —H, —Cl, —I, —Br, —OH, —OR², —NHR³, or—N(R³)₂; each R² is independently selected C_(1 to 4) alkyl or haloalkylgroup; and each R³ is independently selected C_(1 to 4) alkyl orhaloalkyl group.
 31. The method of claim 30, wherein R is a fluoroalkylor perfluoroalkyl group comprising from 6 to 20 carbon atoms.
 32. Themethod of claim 30, wherein R is a fluoroalkyl or perfluoroalkyl groupcomprising from 8 to 20 carbon atoms. 33-46. (canceled)
 47. Arefrigerator shelf surface prepared by the method of claim
 1. 48-49.(canceled)
 50. A refrigerator shelf surface comprising a hydrophobic oroleophobic spill-resistant border, wherein said border comprises aroughened area covalently modified with a silanizing agent that forms aperimeter around at least one area that has a lower hydrophobicity andlower oleophobicity than said border; and wherein said spill resistantborder can withstand at least four washings with soap and water andstill form a perimeter around at least one area that has a lowerhydrophobicity and lower oleophobicity than said border. 51-57.(canceled)
 58. The refrigerator shelf surface of claim 50, wherein saidspill-resistant border provides a retention of up to 5.94 mm of waterafter four washings with soap and water.
 59. The refrigerator shelfsurface of claim 50, wherein said spill-resistant border provides aretention of greater than 2.9 mm of water and less than 5.94 mm of waterafter four washings with soap and water. 60-94. (canceled)